CN111180685B - Spherical oxidation alloy electrode material and preparation method thereof - Google Patents
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Abstract
The invention relates to a spherical oxide alloy electrode material which is characterized by being an oxide alloy lithiation compound doped with one or more metal ions, wherein the surface of the oxide alloy lithiation compound is simultaneously coated with metal oxide which is secondary spherical particles formed by aggregating nano particles, and the chemical general formula is Li4Ti5‑xMxO12·(MyO) can improve the conductivity of the oxide alloy lithium compound by doping one or more metal ions, improve the electrochemical performance, effectively inhibit the reduction and decomposition of the electrolyte and inhibit the gas generation by controlling the condition process and the amount of the metal ions and coating the metal oxide on the surface of the oxide alloy lithium compound, thereby improving the cycling stability of the battery, effectively improving the gas expansion problem and prolonging the cycle life of the high-rate charging.
Description
Technical Field
The invention relates to a preparation method of a spherical oxidation alloy electrode material, belonging to the field of new energy.
Background
At present, lithium ion batteries occupy the largest market share of rechargeable batteries, and are widely applied to civil portable electronic devices such as mobile phones, notebook computers, MP3 and the like, and in recent years, people gradually apply the lithium ion batteries to power devices, and hybrid electric vehicles of the lithium ion batteries and petroleum also enter the market. Most of negative electrode materials adopted by commercial lithium ion batteries are carbon materials, but the negative electrode materials have a fatal problem that when the batteries are charged quickly or overcharged, metal lithium can be separated out from the surfaces of the electrode materials and dendrites are formed to cause short circuit, so that the service life of the products is shortened, and potential safety hazards exist. With the rapid increase of the lithium ion battery market, a novel cathode material with better safety performance is urgently needed.
Spinel type lithium titanate negative electrodeThe lithium ion battery has a three-dimensional diffusion channel for lithium ions, the crystal structure of lithium titanate is hardly changed in the charging and discharging process and is called as a zero-strain material, so that the cycle life of the lithium ion battery taking lithium titanate as a negative electrode can be more than ten thousand times, and is 5-10 times of that of the traditional lithium ion battery. The lithium intercalation potential of the lithium titanate is 1.55V (Vs.Li)+Li), avoids the separation of lithium dendrites under the condition of low potential, reduces the risk of short circuit in the battery, and has extremely high safety. The lithium titanate battery can bear continuous charging and discharging of more than 10 ℃, can be fully charged in 6min, and can meet the requirement of high rate performance of peak and valley regulation of an energy storage power station. The performance of low temperature (-40 ℃) and high temperature (60 ℃) is excellent, and the paint can be used in most regions and environments. Therefore, the lithium titanate battery has the advantages of ultra-long cycle life, higher safety performance, excellent rate performance, high and low temperature performance, lower full life cycle cost and the like, and is particularly suitable for the fields of green energy storage technologies and passenger cars which require long service life, high safety and low cost.
In order to overcome the defects that the existing commercial lithium titanate has poor dispersion processability, poor high-rate charge-discharge cycle life and serious flatulence phenomenon in the using process, CN105406046A discloses a lithium titanate negative electrode material which comprises primary particles, wherein the primary particles are lithium titanate, coating an inner coating layer on the surface of the primary particles, aggregating the primary particles into secondary particles, coating an outer coating layer on the outer surface of the secondary particles, through primary sintering, the excessive growth of particles in the roasting process of raw materials is prevented, the nanocrystallization of primary particles is maintained, the conductivity is increased, the integrity is ensured through secondary coating, the problem of gas expansion is solved, however, the preparation method is complicated in process, so that a scheme for overcoming poor dispersion processability, short cycle life of high-rate charge and discharge and flatulence is further searched, and the problem to be solved is still needed in an industrial process.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a spherical oxidized alloy electrode material which can effectively improve the problem of flatulence and has long service life of a high-rate charging cycle, and also provides a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
subject of the technology 1
The invention provides a spherical oxide alloy electrode material which is one or more metal ion-doped oxide alloy lithiides, wherein the surface of the oxide alloy lithiides is simultaneously coated with metal oxides which are secondary spherical particles formed by aggregation of nano particles, and the chemical general formula of the oxide alloy lithiides is Li4Ti5-xMxO12·(MyO), wherein M is a doped cladding metal ion.
Further, the D50 of the nanoparticles is 100 to 500nm, and the D50 of the spherical particles is 10 to 35 μm.
Furthermore, x + y is more than or equal to 0.05 and less than or equal to 0.2, and y is more than or equal to 0.01 and less than or equal to 0.05.
Further, the doped cladding metal ions M are selected from: any one or more of magnesium, calcium, strontium, barium, yttrium, zirconium, niobium, molybdenum, vanadium, chromium, copper, zinc, silver and cadmium.
Subject matter two
The invention also provides a preparation method of the spherical oxidized alloy electrode, which comprises the following steps:
(1) placing a lithium source, titanium dioxide, an M metal ion source and a medium solution in a reaction kettle, and dispersing to obtain a precursor;
(2) grinding the precursor obtained in the step (1) to obtain a uniformly dispersed nano precursor;
(3) carrying out spray granulation on the nano precursor obtained in the step (2) to obtain a dry spherical precursor;
(4) and (3) placing the dried spherical precursor obtained in the step (3) in air or inert gas atmosphere for presintering and resintering, wherein the presintering temperature is 450-600 ℃, the presintering time is 5-10 h, the resintering temperature is 700-850 ℃, the resintering time is 10-16 h, and cooling to room temperature is carried out.
Further, the molar ratio of the lithium ions to the titanium ions is 4-5: 5, and the molar ratio of the total amount of the M metal ion sources to the titanium ions is 0.05-0.2: 5.
Further, the M metal ion source is selected from any one or a combination of any two or more of nitrate, carbonate, oxalate or oxide.
Further, the lithium source is any one or combination of any two or more of lithium hydroxide monohydrate, lithium carbonate, lithium acetate and lithium nitrate; the titanium dioxide is anatase or rutile titanium dioxide.
Further, the medium solution is any one or combination of any two or more of deionized water, ethanol and ethylene glycol.
Further, the nanoscale precursor D50 is 0.1-0.5 μm, and the dry spherical precursor D50 is 10-35 μm.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
the spherical oxidation alloy electrode material provided by the invention can improve the electronic conductivity of the oxidation alloy lithium compound and improve the electrochemical performance by doping metal ions, and the surface of the oxidation alloy lithium compound is coated with the metal oxide by controlling the condition process and the amount of the metal ions, so that the reduction and decomposition of the electrolyte and the gas generation are effectively inhibited, the cycling stability of the battery is further improved, the problem of gas expansion is effectively improved, and the cycle life of high-rate charging is prolonged.
The preparation method of the invention obtains micron-sized spherical particles with large particle size by controlling the process conditions, and regulates and controls the distribution range of the particle size, thereby realizing reasonable distribution of large, medium and small balls, further improving the tap density and the compaction density of the material and improving the processing performance. By controlling the amount of the doping ions, a part of metal ions can be embedded into the material, and the rest of metal ions form a coating layer on the surface of the material after the calcination process. The doping of metal ions and the formation of an oxide coating layer are realized, secondary coating is not needed, and the process flow is greatly shortened.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD pattern of an oxidized alloy electrode material obtained in example 1 of the present invention;
FIG. 2 is an SEM image of an oxidized alloy electrode material obtained in example 3 of the present invention, wherein the spherical oxidized alloy electrode material is formed by agglomeration of nanoparticles;
FIG. 3 is a TEM image of an oxide alloy electrode material obtained in example 3 of the present invention, in which a coating layer is visible on the surface of primary particles of the spherical oxide alloy electrode material;
FIG. 4 is a TEM image of the oxide alloy electrode material obtained in comparative example 1 of the present invention, and it can be seen that no coating layer is found on the surface of the primary particles of the spherical oxide alloy electrode material.
FIG. 5 is a TEM image of the electrode material obtained in comparative example 2 of the present invention, and it can be seen that no coating layer is found on the surface of the primary particles of the spherical electrode material.
Detailed Description
The spherical oxidized alloy electrode material is oxidized alloy lithiation compound doped with one or more metal ions, the surface of the oxidized alloy lithiation compound is simultaneously coated with metal oxide which is secondary spherical particles formed by aggregating nano particles, and the chemical general formula is Li4Ti5-xMxO12·(MyO), wherein M is a doped cladding metal ion.
In the present invention, the D50 of the nanoparticle is 100 to 500nm, the D50 of the spherical particle is 10 to 35 μm, the D50 of the nanoparticle is 500nm, and the D50 of the spherical particle is 35 μm. The D50 of the nanoparticles was 100nm, and the D50 of the spherical particles was 10 μm.
In the invention, x + y is more than or equal to 0.05 and less than or equal to 0.2, further, x + y is more than or equal to 0.08 and less than or equal to 0.18, and further, x + y is more than or equal to 0.12 and less than or equal to 0.15.
In the invention, y is more than or equal to 0.01 and less than or equal to 0.05, further, y is more than or equal to 0.01 and less than or equal to 0.04, and further, y is more than or equal to 0.02 and less than or equal to 0.03.
In the present invention, the doped cladding metal ion M is selected from: any one or more of magnesium, calcium, strontium, barium, yttrium, zirconium, niobium, molybdenum, vanadium, chromium, copper, zinc, silver and cadmium.
The invention also provides a preparation method of the spherical oxidation alloy electrode material, which comprises the following steps:
(1) placing a lithium source, titanium dioxide, an M metal ion source and a medium solution in a reaction kettle, and dispersing to obtain a precursor;
(2) grinding the precursor obtained in the step (1) to obtain a uniformly dispersed nano precursor;
(3) carrying out spray granulation on the nano precursor obtained in the step (2) to obtain a dry spherical precursor;
(4) and (3) placing the dried spherical precursor obtained in the step (3) in air or inert gas atmosphere for presintering and resintering, wherein the presintering temperature is 450-600 ℃, the presintering time is 5-10 h, the resintering temperature is 700-850 ℃, the resintering time is 10-16 h, and cooling to room temperature is carried out.
In the present invention, the starting materials used are commercially available products well known to those skilled in the art, unless otherwise specified.
In the present invention, the molar ratio of the lithium ion to the titanium ion is 4 to 5:5, further 4.2 to 4.8:5, and further 4.2 to 4.6: 5. The molar ratio of the total amount of the M metal ion sources to the titanium ions is 0.05-0.2: 5, further 0.08-0.18: 5, further 0.12-0.15: 5.
In the present invention, the M metal ion source is selected from one or more of nitrate, carbonate, oxalate or oxide.
In the present invention, the lithium source is one or more of lithium hydroxide monohydrate, lithium carbonate, lithium acetate and lithium nitrate.
In the present invention, the titanium dioxide is anatase or rutile titanium dioxide.
In the invention, the medium solution is one or more of deionized water, ethanol and glycol.
Mixing and grinding a lithium source, titanium dioxide and an M metal ion source, wherein the grinding time is preferably 3-8 hours, and further preferably 4-6 hours; the rotation speed of the grinding is preferably 600 to 2200r/min, and more preferably 1000 to 2000 r/min. In the invention, the grinding can be realized by high-intensity grinding in a high-energy ball mill or a nano sand mill, and the specific model is not required, and the method is well known by the technical personnel in the field. In the grinding process, the grinding time and speed are controlled, the raw materials are mixed, and the nano precursor with the particle size of 100-500 nm is obtained.
And after obtaining the nano precursor, carrying out spray granulation, wherein the air inlet temperature of spray drying is 200-220 ℃, the air outlet temperature is 80-100 ℃, and the centrifugal rotating speed is 20000-40000 r/min.
The invention carries out presintering and resintering on the secondary spherical particles in sequence, and obtains the spherical oxidation alloy electrode material after being cooled at room temperature and being crushed and sieved. In the invention, the pre-sintering temperature is 450-600 ℃, preferably 480-580 ℃, and further preferably 500-550 ℃; the pre-sintering time is 5-10 h, preferably 6-8 h, in the invention, the pre-sintering temperature is preferably reached in a constant temperature rise mode, and the temperature rise rate is preferably 1-5 ℃/min, preferably 4.5-4.8 ℃/min.
In the invention, the temperature of the re-sintering is 700-850 ℃, preferably 750-800 ℃, and further preferably 770-780 ℃; the time for the re-sintering is 10-16 h, preferably 12-14 h. In the present invention, the temperature of the re-sintering is preferably obtained by raising the temperature of the pre-sintering; the heating rate is preferably 1 to 5 ℃/min, and more preferably 4.5 to 4.8 ℃/min.
In the invention, the crushing and sieving are 300-mesh sieving.
In the presintering and resintering processes, doping of metal ions is formed; meanwhile, partial metal oxide remains on the surface to form a coating structure, and the spherical oxidation alloy electrode material is obtained.
In the present invention, the gas atmosphere during sintering is not particularly limited, and may be an air atmosphere or an inert gas atmosphere.
In order to further illustrate the present invention, the following detailed description of the spherical oxidized alloy electrode material and the preparation method thereof provided by the present invention is made with reference to the drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
Material proportioning: the metal ions are Mg, the molar ratio of the titanium ions to the metal ions is 5:0.2, and the molar ratio of the lithium ions to the titanium ions is 4: 5.
(1) And (2) placing the lithium hydroxide monohydrate, the titanium dioxide, the nano magnesium oxide and the ethanol solution into a reaction kettle according to the proportion, wherein the solid-to-liquid ratio is 1:2, and continuously stirring and ultrasonically dispersing for 4 hours at the rotating speed of 200r/min to obtain the precursor.
(2) And (2) placing the precursor obtained in the step (1) into a high-energy ball mill for high-strength ball milling at the rotating speed of 1500r/min until D50 is 0.5 mu m, so as to obtain the uniformly dispersed nano precursor.
(3) And (3) carrying out spray granulation on the nano precursor obtained in the step (2), wherein the air inlet temperature is 200 ℃, the air outlet temperature is controlled at 100 ℃, and the rotating speed is 20000r/min, so as to obtain a dry spherical precursor, and the D50 of the nano particles with the D50 of 0.5 mu m is aggregated into secondary spherical particles with the D50 of 35 mu m.
(4) Placing the secondary spherical particles in the step (3) in an air atmosphere for high-temperature calcination, firstly calcining at the temperature of 450 ℃ for 10h, then uniformly heating to the temperature of 700 ℃ for calcination for 16h, and finally naturally cooling to room temperature to obtain Li4Ti4.82Mg0.18O12·(Mg0.02O), crushing and sieving by a 300-mesh sieve.
Example 2
Material proportioning: the metal ions are Zn and Ag, the molar ratio of the two metal ions satisfies Zn: Ag =1:1, the molar ratio of the titanium ions to the two metal ions is 5:0.18, and the molar ratio of the lithium ions to the titanium ions is 4.2: 5.
(1) Placing a lithium source, titanium dioxide, zinc acetate, silver nitrate and an ethanol solution in a reaction kettle according to the proportion, wherein the solid-to-liquid ratio is 1: and 3, continuously stirring and ultrasonically dispersing for 4.5h at the rotating speed of 200r/min to obtain the precursor.
(2) And (2) placing the precursor obtained in the step (1) into a high-energy ball mill for high-strength ball milling for 5 hours at the rotating speed of 1500r/min until D50 is 0.5 mu m, and obtaining the uniformly dispersed nano precursor.
(3) And (3) carrying out spray granulation on the nano precursor obtained in the step (2), wherein the air inlet temperature is 200 ℃, the air outlet temperature is controlled at 85 ℃, and the rotating speed is 20000r/min, so as to obtain a dry spherical precursor, and the D50 formed by aggregation of nano particles with the D50 of 0.1 mu m is secondary spherical particles with the D50 of 20 mu m.
(4) Placing the secondary spherical particles in the step (3) in an air atmosphere for high-temperature calcination, firstly raising the temperature to 450 ℃ at a constant speed for 10 hours, then raising the temperature to 750 ℃ at a constant speed for 14 hours, and finally naturally cooling to room temperature to obtain Li4Ti4.84Zn0.08Ag0.08O12·(Zn0.01Ag0.01O), crushing and sieving by a 300-mesh sieve.
Example 3
Material proportioning: the metal ions are V, Nb and Cu, the molar ratio of the three metal ions satisfies V: Nb: Cu =1:1:1, the molar ratio of the titanium ions to the three metal ions is 5:0.15, and the molar ratio of the lithium ions to the titanium ions is 4.2: 5.
(1) Putting lithium hydroxide monohydrate, titanium dioxide, vanadium pentoxide, niobium oxalate hydrate, copper nitrate and ethanol solution into a reaction kettle, wherein the solid-to-liquid ratio is 1:2, stirring and ultrasonic dispersing for 5 hours continuously, and rotating at the speed of 200r/min to obtain the precursor.
(2) And (2) placing the precursor obtained in the step (1) in a high-energy ball mill for high-strength ball milling for 4.5h at the rotating speed of 1800r/min until D50 is 0.1 mu m, and obtaining the uniformly dispersed nano precursor.
(3) And (3) carrying out spray granulation on the nano precursor obtained in the step (2), wherein the air inlet temperature is 200 ℃, the air outlet temperature is controlled at 80 ℃, and the rotating speed is 40000r/min, so as to obtain a dry spherical precursor, and the D50 formed by aggregation of nano particles with the D50 of 0.1 mu m is secondary spherical particles with the D50 of 10 mu m.
(4) Placing the secondary spherical particles in the step (3) in an air atmosphere for high-temperature calcination, firstly heating to 600 ℃ at a constant speed for 5 hours, then heating to 700 ℃ at a constant speed for 13 hours, and finally naturally cooling to room temperature to obtain Li4Ti4.88V0.04Nb0.04Cu0.04O12·(V0.01Nb0.01Cu0.01O), crushing and sieving by a 300-mesh sieve.
Example 4
Material proportioning: the metal ions are Sr, Zr and Mo, the molar ratio of the three metal ions satisfies Sr: Zr: Mo =1:1:1, the molar ratio of the titanium ions to the three metal ions is 5:0.12, and the molar ratio of the lithium ions to the titanium ions is 4.2: 5.
(1) Putting lithium hydroxide monohydrate, titanium dioxide, strontium acetate, zirconium acetate, molybdenum trioxide and ethanol solution into a reaction kettle, wherein the solid-to-liquid ratio is 1:2, and continuously stirring and ultrasonically dispersing for 5 hours at the rotating speed of 200r/min to obtain a precursor.
(2) And (2) placing the precursor obtained in the step (1) into a high-energy ball mill for high-strength ball milling for 4.5h at the rotating speed of 2000r/min until D50 is 0.1 mu m, so as to obtain the uniformly dispersed nano precursor.
(3) And (3) carrying out spray granulation on the nano precursor obtained in the step (2), wherein the air inlet temperature is 220 ℃, the air outlet temperature is controlled at 90 ℃, and the rotating speed is 30000r/min, so as to obtain a dry spherical precursor, and the D50 formed by aggregation of nano particles with the D50 of 0.1 mu m is secondary spherical particles with the D50 of 10 mu m.
(4) Placing the secondary spherical particles in the step (3) in an air atmosphere for high-temperature calcination, firstly heating to 600 ℃ at a constant speed for 5 hours, then heating to 850 ℃ at a constant speed for 10 hours, and finally naturally cooling to room temperature to obtain Li4Ti4.91Sr0.03Zr0.03Mo0.03O12·(Sr0.01Zr0.01Mo0.01O), crushing and sieving by a 300-mesh sieve.
Comparative example 1
(1) Placing a lithium source, titanium dioxide and an ethanol solution in a reaction kettle, and continuously stirring and ultrasonically dispersing for 5 hours, wherein the molar ratio of lithium ions to titanium ions is 4:5, the solid-liquid ratio is 1:2, rotating at the speed of 200r/min to obtain the liquid-phase precursor.
(2) And (2) placing the precursor obtained in the step (1) in a high-energy ball mill for high-strength ball milling for 4 hours at a rotating speed of 1600r/min until D50 is 0.5 mu m, and obtaining the uniformly dispersed nano precursor.
(3) And (3) carrying out spray granulation on the nano precursor obtained in the step (2), controlling the air inlet temperature to be 200 ℃, the air outlet temperature to be 100 ℃ and the rotating speed to be 18000r/min, so as to obtain a dry spherical precursor, wherein the D50 formed by aggregation of nano particles with the D50 of 0.1 mu m is secondary spherical particles with the D50 of 10 mu m.
(4) And (3) placing the dried spherical precursor obtained in the step (3) in an air atmosphere for high-temperature calcination, firstly heating to 600 ℃ at a constant speed for 5 hours, then heating to 850 ℃ at a constant speed for 10 hours, finally naturally cooling to room temperature, crushing and sieving with a 300-mesh sieve.
Comparative example 2
Material proportioning: the metal ions are Sr and Al, the molar ratio of the two metal ions satisfies Sr: Al =9:1, the molar ratio of the titanium ions to the two metal ions is 6:1, and the molar ratio of the lithium ions to the titanium ions is 2.05: 6.
(1) And placing nano lithium carbonate, titanium dioxide, nano aluminum oxide, strontium carbonate and deionized water in a reaction kettle, ball-milling and mixing for 2 hours at a solid-liquid ratio of 1:2 and a rotation speed of 200r/min to obtain a liquid-phase precursor.
(2) And (2) performing spray granulation on the precursor obtained in the step (1), wherein the air inlet temperature is 200 ℃, the air outlet temperature is controlled at 100 ℃, and the rotating speed is 30000r/min, so as to obtain the dry spherical precursor.
(3) And (3) placing the dried spherical precursor obtained in the step (2) in an air atmosphere for high-temperature calcination, firstly heating to 400 ℃ at a constant speed for calcination for 12h, then heating to 900 ℃ at a constant speed for calcination for 18h, finally naturally cooling to room temperature, crushing and sieving with a 300-mesh sieve.
Experimental examples electrochemical test
Uniformly mixing the prepared oxidized alloy electrode material, PVDF (polyvinylidene fluoride) as an adhesive and sp as a conductive agent according to a ratio of 85:10:5 to obtain electrode slurry, then coating the slurry on a copper foil current collector, drying, cutting the whole electrode slice into electrode slices with the diameter of 1.0cm, drying the electrode slices in a vacuum drying oven at 105 ℃ for 24 hours to remove trace moisture and solvents in the electrode slices, and transferring the electrode slices to a glove box to assemble the CR2032 button cell. The CR2032 button cell uses an oxidized alloy electrode plate as a positive electrode, a lithium plate as a negative electrode, a diaphragm as Celgrad 2400, and an electrolyte as a lithium hexafluorophosphate solution, and the assembled cell is left to stand for 24 hours at room temperature and then undergoes a constant current charge-discharge rate test, and the results are shown in table 1.
Uniformly mixing the prepared oxidized alloy electrode material, PVDF (polyvinylidene fluoride) as an adhesive and sp as a conductive agent according to a ratio of 85:10:5 to obtain electrode slurry, then coating the slurry on a copper foil current collector, drying, cutting the whole electrode plate into electrode plates of 5.0cm multiplied by 10.0cm, drying the electrode plates in a vacuum drying oven at 105 ℃ for 24 hours to remove trace moisture and solvents in the electrode plates, and transferring the electrode plates into a glove box to be made into a flexible package battery together with a lithium cobaltate material. The soft package battery takes an oxidized alloy electrode plate as a negative electrode, a lithium cobaltate electrode plate as a positive electrode, a diaphragm is Celgrad 2400, an electrolyte is a lithium hexafluorophosphate solution, the assembled battery is kept stand for 24 hours at room temperature and then subjected to a circular inflation test, and the result is shown in Table 2.
Table 1 constant current charge and discharge multiplying power test results
The results show that the constant current charge-discharge rate capacitance of the invention in the 1-3V ranges is obviously superior to that of the comparative examples 1 and 2 in the examples 1, 2, 3 and 4.
TABLE 25C bloating degree and capacity retention after 5000 times of large-rate charge and discharge
The result shows that the material provided by the invention has obviously reduced flatulence degree and better capacity retention rate.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. The spherical oxide alloy electrode material is characterized by being oxide alloy lithiation doped with one or more metal ions, wherein the surface of the oxide alloy lithiation is simultaneously coated with metal oxide which is secondary spherical particles formed by aggregating nano particles, and the chemical general formula of the oxide alloy lithiation is Li4Ti5-xMxO12·(MyO), M is doped cladding metal ion; wherein x + y is more than or equal to 0.05 and less than or equal to 0.2, and y is more than or equal to 0.01 and less than or equal to 0.05;
it is prepared by the following method:
(1) placing a lithium source, titanium dioxide, an M metal ion source and a medium solution in a reaction kettle, and dispersing to obtain a precursor;
(2) grinding the precursor obtained in the step (1) to obtain a uniformly dispersed nano precursor;
(3) carrying out spray granulation on the nano precursor obtained in the step (2) to obtain a dry spherical precursor;
(4) and (3) placing the dried spherical precursor obtained in the step (3) in air or inert gas atmosphere for presintering and resintering, wherein the presintering temperature is 450-600 ℃, the presintering time is 5-10 h, the resintering temperature is 700-850 ℃, the resintering time is 10-16 h, and cooling to room temperature is carried out.
2. The spherical oxide alloy electrode material as claimed in claim 1, wherein the D50 of the nanoparticles is 100-500 nm, and the D50 of the spherical particles is 10-35 μm.
3. The spherical oxide alloy electrode material as claimed in claim 1, wherein the doped cladding metal ions M are selected from: one or the combination of any two of magnesium, calcium, strontium, barium, yttrium, zirconium, niobium, molybdenum, vanadium, chromium, copper, zinc, silver and cadmium.
4. The spherical oxide alloy electrode material as claimed in claim 1, wherein the molar ratio of lithium ions to titanium ions is 4-5: 5, and the molar ratio of the total amount of M metal ion sources to titanium ions is 0.05-0.2: 5.
5. The spherical oxidation alloy electrode material as claimed in claim 1, wherein the M metal ion source is selected from any one or a combination of any two or more of nitrate, carbonate, oxalate or oxide.
6. The spherical oxide alloy electrode material as claimed in claim 1, wherein the lithium source is any one or a combination of any two or more of lithium hydroxide monohydrate, lithium carbonate, lithium acetate and lithium nitrate; the titanium dioxide is anatase or rutile titanium dioxide.
7. The spherical oxidation alloy electrode material as claimed in claim 1, wherein the dielectric solution is one or a combination of two or more of deionized water, ethanol and ethylene glycol.
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