CN109037602A - A kind of double oxide cladding tertiary cathode material and preparation method thereof - Google Patents
A kind of double oxide cladding tertiary cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of double oxide cladding tertiary cathode materials and preparation method thereof, belong to technical field of lithium ion.The preparation method includes: that (1) tertiary cathode material is added in organic solvent, and ultrasonic disperse obtains the first dispersion liquid；(2) titanium source and silicon source are added to step (1) identical organic solvent, ultrasonic disperse obtains the second dispersion liquid；(3) the first dispersion liquid and the second dispersion liquid are mixed, water is added dropwise according to stoichiometric ratio, is stirred to react, then be evaporated all solvents, obtains composite material precursor；(4) composite material precursor, which is calcined, is made double oxide cladding tertiary cathode material.Guarantee that final whole clad is uniformly distributed using the different rate of film builds presented in silica and titanium oxide high-temperature burning process, one layer of clad is collectively formed in two oxides, the effect of 1+1 > 2 is played to the cladding of positive electrode, not only the cyclical stability of material had been improved, but also has improved the high rate performance of material.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of double oxide cladding tertiary cathode material and its
Preparation method.
Background technique
The problems such as with energy crisis and environmental pollution, becomes increasingly conspicuous, Sustainable Development new energy, builds low-carbon
Society becomes the task of top priority.Lithium ion battery is concerned as a kind of novel high-energy green battery.Stratiform nickel-cobalt-manganese ternary is just
Pole material is a kind of material of great development prospect, with LiCoO2、LiNiO2、LiMnO2It compares, at low cost, capacity is big, follows
The advantages that ring performance is good, thermostabilization is good, structure is more stable.
Although nickel-cobalt-manganternary ternary anode material has many advantages, such as, which still has certain problem, such as electricity
Solution liquid has certain corrosiveness to electrode material, makes the capacity attenuation of material, influences the cyclical stability of material.So right
The modification of positive electrode becomes the important means for improving material electrochemical performance, wherein cladding is simple effective method the most.
The presence of clad can maintain the surface texture stability of its own, avoid the direct contact between active material and electrolyte, suppression
The dissolution of prepared material transition metal element under high condition, so as to improve the capacity retention ratio of positive electrode.
Surface cover matter for ternary lithium ion anode material includes the SiO of single layer2、B2O3、Al2O3、AlPO4、
AlF3、LiAlO2、ZrO2, carbon, graphene, V2O5、Y2O3Deng.Currently, improving layered cathode using the cladding of metal oxide
The research of material property is more.
Application publication number is that the patent document of 103972499 A of CN discloses a kind of nickel cobalt lithium aluminate anode material of modification
Material, by LiNi1-a-bCoaAlbO2Powder and nano-TiO2Powder sprays into coating unit simultaneously according to a certain mass ratio, through overcharging
Dispersion, absorption and recombination make nano-TiO2Powder is evenly coated at LiNi1-a-bCoaAlbO2Enter collection device after powder surface
In to get to modified LiNi1-a-bCoaAlbO2/TiO2Positive electrode.It is coated, is not generated during cladding useless using dry method
Liquid is not necessarily to high temperature sintering simultaneously, can reduce energy consumption and cost.
Application publication number is that the patent document of CN106299320A discloses a kind of modified nickle cobalt lithium manganate tertiary cathode material
The preparation method of material, after the aqueous nickel-cobalt lithium manganate material in surface, titanium source and organic solvent are mixed, hydrolysis obtains nickel
Cobalt manganic acid lithium composite material obtains the nickel-cobalt lithium manganate material that titanium dioxide layer is coated with to surface after calcining.
Single cladding substance can promote the performance of material really, but can not reach high rate performance and cycle performance
While promoted.In addition single clad mostly uses coarse ball-milling method and the precipitation method in cladding means, and cladding is not achieved
The requirement that layer is evenly distributed.
Summary of the invention
It is existing to overcome the purpose of the present invention is to provide a kind of preparation method of double oxide cladding tertiary cathode material
The problems such as being unevenly distributed existing for single oxide clad in technology.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of double oxide cladding tertiary cathode material, comprising the following steps:
(1) tertiary cathode material is added in organic solvent, ultrasonic disperse obtains the first dispersion liquid；
(2) titanium source and silicon source are added to step (1) identical organic solvent, ultrasonic disperse obtains the second dispersion
Liquid；
(3) the first dispersion liquid and the second dispersion liquid are uniformly mixed, are gone according to the stoichiometric ratio dropwise addition of coating layer material
Ionized water is stirred to react, then is evaporated all solvents, obtains composite material precursor；
(4) composite material precursor, which is calcined, is made double oxide cladding tertiary cathode material.
Titanium oxide and silica are generated using titanium source and silicon source in preparation method of the present invention, tertiary cathode material is protected
Shield, the different rate of film build significant increases that are showed in high-temperature burning process by both oxides are final whole
The uniformity coefficient of clad.One layer of clad is collectively formed in two oxides, and the effect of 1+1 > 2 is played to the cladding of material.
The tertiary cathode material can be nickel-cobalt-manganternary ternary anode material (NCM), nickel cobalt aluminium tertiary cathode material
(NCA)。
Preferably, the tertiary cathode material is nickel-cobalt-manganternary ternary anode material, chemical molecular formula in step (1)
For Li (Ni1-x-yCoxMny)O2, wherein 0 < x < 0.4,0 < y < 1.The molar ratio of nickel cobalt manganese is 6:2:2,5:2:3,4:4:2 or 1:1:
1。
Preferably, the tertiary cathode material partial size is 5-15 μm.
The organic solvent is one or more of methanol, ethyl alcohol, isopropanol.
Preferably, the mass volume ratio of tertiary cathode material and organic solvent is 3g:30-100mL.More preferably, nickel
The mass volume ratio of cobalt-manganese ternary positive electrode and organic solvent is 3g:50mL.
Preferably, in step (2), the titanium source be one of butyl titanate, isopropyl titanate, titanium tetrachloride or
It is several.
Preferably, the silicon source is ethyl orthosilicate, hexamethyldisiloxane, three second of 3- aminopropyl in step (2)
One or more of oxysilane (APTES).
Preferably, the titanium source is 3:2-8 with molar ratio of the silicon source in terms of silicon in terms of titanium in step (2).
More preferably, the molar ratio of the two is 3:2.
Preferably, the mass ratio of tertiary cathode material and titanium source in terms of titanium is 100:1.
Preferably, the condition being stirred to react: temperature is 50-120 DEG C, revolving speed 500-1000r/ in step (3)
Min, time 2-5h.More preferably, in 70 DEG C of heating stirrings, revolving speed 700r/min reacts 2h.
Preferably, in step (4), the calcination condition are as follows: 300-800 is warming up to the rate of 1-10 DEG C/min
DEG C, reaction time 2-10h.Heating rate is slower, and it is more smooth to be formed by film.Too fast the phenomenon that will appear clad rupture.
More preferably, 400 DEG C are warming up to the rate of 5 DEG C/min, reaction time 3h.
It is a further object to provide a kind of double oxide as made from preparation method cladding ternarys just
Pole material, including tertiary cathode material and clad, the clad are made of silica and titanium oxide, and the mass ratio of the two is
1:0.5-2, the clad with a thickness of 1-10nm.
One layer of clad is collectively formed in silica and titanium oxide, compared to the ternary of single silica or titanium-oxide-coated
Positive electrode, the circulation and high rate performance of composite material provided by the invention are promoted.
It is that the present invention has the utility model has the advantages that
(1) silica and titanium oxide formation clad protect tertiary cathode material in preparation method provided by the invention
Shield, the different rate of film builds that two oxides is presented in high-temperature burning process guarantee that final whole clad uniformly divides
Cloth.
A small amount of titanium oxide reacts to form lithium titanyl fast-ionic conductor with positive electrode lithium remained on surface, is beneficial to material
High rate performance promotion；Silica is good tertiary cathode covering material, its suppression for material and electrolyte side reaction
Fixture has remarkable result.One layer of clad is collectively formed in two oxides, and the effect of 1+1 > 2 is played to the cladding of positive electrode,
Not only the cyclical stability of material had been improved, but also has improved the high rate performance of material, where the advantage for embodying double oxide cladding.
(2) button cell is assembled using double oxide provided by the invention cladding tertiary cathode material, in 2.75-4.3V,
Under 0.5C, discharge capacity is 160.1mAh/g for the first time, and after circulation 100 is enclosed, capacity 152.8mAh/g, capacity retention ratio is up to
95.4%；And respectively under the multiplying power of 0.2C, 0.5C, 1C, 2C, 5C, discharge capacity 171.2mAh/g, 165.1mAh/g,
158.3mAh/g,149.8mAh/g,134.2mAh/g.The ternary coated compared to uncoated ternary material and single oxide
Positive electrode, circulation and high rate performance are promoted.
(3) preparation method process provided by the invention is simple, low in cost, is suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the XRD diagram of the nickel-cobalt-manganternary ternary anode material of the cladding of double oxide made from embodiment 1.
Fig. 2 is the SEM figure of the nickel-cobalt-manganternary ternary anode material of the cladding of double oxide made from embodiment 1.
Fig. 3 is the TEM figure of the nickel-cobalt-manganternary ternary anode material of the cladding of double oxide made from embodiment 1.
Fig. 4 is the nickel-cobalt-manganternary ternary anode material comparison nickel-cobalt-manganese ternary anode of the cladding of double oxide made from embodiment 1
Cycle performance figure of the material under 0.5C charge and discharge.
Fig. 5 is the nickel-cobalt-manganternary ternary anode material comparison nickel-cobalt-manganese ternary anode of the cladding of double oxide made from embodiment 1
Discharge curve performance map of material under the conditions of 0.2C, 0.5C, 1C, 2C, 5C multiplying power.
Specific embodiment
The present invention will be further described below with reference to examples.Following embodiment is only intended to clearly illustrate this
The performance of invention, and the following examples cannot be limited only to.
Embodiment 1
A kind of preparation method of double oxide cladding nickel-cobalt-manganternary ternary anode material:
(1) by 3g nickel-cobalt-manganternary ternary anode material Li (Ni0.6Co0.2Mn0.2)O2It is scattered in 50mL anhydrous methanol ultrasonic
Then 30min stirs to get turbid solution；
(2) butyl titanate of 93.09mg and 34.70mg ethyl orthosilicate TEOS are dispersed in 10mL anhydrous methanol and are surpassed
Sound makes it be uniformly dispersed to obtain dispersion liquid；
(3) dispersion liquid obtained in step (2) is poured into step (1) resulting turbid solution, 70 DEG C of heating stirrings, revolving speed
For 700r/min, reacts 2h and the deionized water of stoichiometric ratio is slowly added dropwise in the process.Then temperature heating is increased to steam
It is dry, take out material dried for standby；
(4) covering material presoma obtained in step (3) is put into 400 DEG C of calcining 3h in Muffle furnace, 5 DEG C/min, obtained
Nickel-cobalt-manganternary ternary anode material is coated to final silica and titanium oxide two oxides.
In the nickel-cobalt-manganternary ternary anode material of double oxide cladding, wherein the mass percent of double oxide is 1wt%,
The mass ratio of silica and titanium oxide is 1:2, the uniform clad that double oxide is formed with a thickness of 2nm.
As shown in Figure 1, resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention in structure simultaneously
There is no significantly changing.
As shown in Fig. 2, resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention be partial size be 8~
12 μm of spheric granules.
As shown in figure 3, the cladding thickness of the resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention
Degree is about 2nm.
The assembling of battery: the cladding nickel-cobalt-manganternary ternary anode material of titanium phosphate lithium obtained by the 0.45g embodiment of the present invention is weighed, is added
Enter that 0.025g conductive carbon black makees conductive agent and 0.025g PVDF (Kynoar) makees binder, is coated in aluminium foil after mixing
On positive plate is made, be diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC (volume ratio 1:1) is electrolyte, is assembled into the button cell of CR2025.
As shown in figure 4, the battery assembled is in 2.5~4.3V voltage range, under 0.5C multiplying power, in 2.75~4.3V,
Under 0.5C, discharge capacity is 160.1mAh/g for the first time, and after circulation 100 is enclosed, capacity 152.8mAh/g, capacity retention ratio is up to
95.4%.
If Fig. 5 is respectively under the multiplying power of 0.2C, 0.5C, 1C, 2C, 5C, discharge capacity 171.2mAh/g, 165.1mAh/
g、158.3mAh/g、149.8mAh/g、134.2mAh/g。
Embodiment 2
A kind of preparation method of double oxide cladding nickel-cobalt-manganternary ternary anode material:
(1) by 3g nickel-cobalt-manganternary ternary anode material Li (Ni0.4Co0.4Mn0.2)O2It is scattered in 30mL dehydrated alcohol ultrasonic
Then 30min stirs to get turbid solution；
(2) the metatitanic acid butene esters and 26.03mgTEOS of 32.1mg are dispersed in ultrasound in 30mL dehydrated alcohol makes its dispersion
Uniformly obtain dispersion liquid；
(3) dispersion liquid obtained in step (2) is poured into step (1) resulting turbid solution, 50 DEG C of heating stirrings, revolving speed
For 1000r/min, 5h is reacted, in the process, the deionized water of stoichiometric ratio is slowly added dropwise, temperature heating is increased and is evaporated,
Take out material dried for standby；
(4) covering material presoma obtained in step (3) is put into Muffle furnace 300 DEG C of calcining 10h, 1 DEG C/min.?
Nickel-cobalt-manganternary ternary anode material is coated to final double oxide.
In the nickel-cobalt-manganternary ternary anode material of double oxide cladding, the mass percent of double oxide is 0.5wt%,
The mass ratio of middle silica and titanium oxide is 1:1, the uniform clad that double oxide is formed with a thickness of 1nm.
Through examining, resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention in structure not
Apparent variation occurs.
Through examining, it is 8~12 μ that the resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention, which is partial size,
The spheric granules of m.
Through examining, the coating thickness of the resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention is big
About 1nm.
The assembling of battery: the cladding nickel-cobalt-manganternary ternary anode material of titanium phosphate lithium obtained by the 0.45g embodiment of the present invention is weighed, is added
Enter that 0.025g conductive carbon black makees conductive agent and 0.025g PVDF (Kynoar) makees binder, is coated in aluminium foil after mixing
On positive plate is made, be diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC (volume ratio 1:1) is electrolyte, is assembled into the button cell of CR2025, the battery assembled 2.5~
In 4.3V voltage range, under 0.5C multiplying power, at 2.75~4.3V, 0.5C, discharge capacity is 163.1mAh/g, circulation for the first time
After 100 circles, capacity 150.1mAh/g, capacity retention ratio is up to 92.0%.
Respectively under the multiplying power of 0.2C, 0.5C, 1C, 2C, 5C, discharge capacity 174.1mAh/g, 166.3mAh/g,
150.2mAh/g、142.1mAh/g、125.5mAh/g。
Embodiment 3
A kind of preparation method of double oxide cladding nickel-cobalt-manganternary ternary anode material:
(1) by 3g nickel-cobalt-manganternary ternary anode material Li (Ni0.5Co0.2Mn0.3)O2It is scattered in 100mL dehydrated alcohol ultrasonic
Then 30min stirs to get turbid solution；
(2) the metatitanic acid butene esters and 138.89mgTEOS of 85.08mg are dispersed in ultrasound in 10mL dehydrated alcohol makes its point
It dissipates and uniformly obtains dispersion liquid；
(3) dispersion liquid obtained in step (2) is poured into step (1) resulting turbid solution, 120 DEG C of heating stirrings, is turned
Speed is 1000r/min, and the deionized water of stoichiometric ratio is slowly added dropwise in the process in reaction 2h.Then temperature heating is increased
It is evaporated, takes out material dried for standby；
(4) covering material presoma obtained in step (3) is put into Muffle furnace 800 DEG C of calcining 2h, 10 DEG C/min.?
Nickel-cobalt-manganternary ternary anode material is coated to final double oxide.
In the nickel-cobalt-manganternary ternary anode material of double oxide cladding, the mass percent of double oxide is 2wt%, wherein
The mass ratio of silica and titanium oxide is 2:1, the uniform clad that double oxide is formed with a thickness of 10nm；
Through examining, resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention in structure not
Apparent variation occurs.
Through examining, it is 8~12 μ that the resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention, which is partial size,
The spheric granules of m.
Through examining, the coating thickness of the resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention is big
About 10nm.
The assembling of battery: the cladding nickel-cobalt-manganternary ternary anode material of titanium phosphate lithium obtained by the 0.45g embodiment of the present invention is weighed, is added
Enter that 0.025g conductive carbon black makees conductive agent and 0.025g PVDF (Kynoar) makees binder, is coated in aluminium foil after mixing
On positive plate is made, be diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC (volume ratio 1:1) is electrolyte, is assembled into the button cell of CR2025, the battery assembled 2.5~
In 4.3V voltage range, under 0.5C multiplying power, at 2.75~4.3V, 0.5C, discharge capacity is 155.4mAh/g, circulation for the first time
After 100 circles, capacity 150.2mAh/g, capacity retention ratio is up to 96.6%.
Respectively under the multiplying power of 0.2C, 0.5C, 1C, 2C, 5C, discharge capacity 169.2mAh/g, 161.8mAh/g,
142.3mAh/g、133.4mAh/g、111.3mAh/g。
Embodiment 4
A kind of preparation method of double oxide cladding nickel-cobalt-manganternary ternary anode material:
(1) by 3g nickel-cobalt-manganternary ternary anode material Li (Ni0.33Co0.33Mn0.33)O2It is scattered in 30mL dehydrated alcohol ultrasonic
Then 30min stirs to get turbid solution.
(2) the metatitanic acid butene esters and 173.5mgTEOS of 428mg are dispersed in ultrasound in 10mL dehydrated alcohol keeps its dispersion equal
It is even to obtain dispersion liquid.
(3) dispersion liquid obtained in step (2) is poured into step (1) resulting turbid solution.70 DEG C of heating stirrings, revolving speed
For 700r/min, 2h is reacted, the deionized water of stoichiometric ratio is slowly added dropwise in the process, temperature heating is increased and is evaporated.It takes
Material dried for standby out.
(4) covering material presoma obtained in step (3) is put into Muffle furnace 400 DEG C of calcining 3h, 5 DEG C/min.?
Nickel-cobalt-manganternary ternary anode material is coated to final double oxide.
In the nickel-cobalt-manganternary ternary anode material of double oxide cladding, the mass percent of double oxide is 5wt%, wherein
The mass ratio of silica and titanium oxide is 1:2.The clad that double oxide is formed with a thickness of 2.2nm；
Through examining, resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention in structure not
Apparent variation occurs.
Through examining, it is 8~12 μ that the resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention, which is partial size,
The spheric granules of m.
Through examining, the coating thickness of the resulting double oxide cladding nickel-cobalt-manganternary ternary anode material of the embodiment of the present invention is big
About 1.2nm.But some are not coated completely.
The assembling of battery: the cladding nickel-cobalt-manganternary ternary anode material of titanium phosphate lithium obtained by the 0.45g embodiment of the present invention is weighed, is added
Enter that 0.025g conductive carbon black makees conductive agent and 0.025g PVDF (Kynoar) makees binder, is coated in aluminium foil after mixing
On positive plate is made, be diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC (volume ratio 1:1) is electrolyte, is assembled into the button cell of CR2025, the battery assembled 2.5~
In 4.3V voltage range, under 0.5C multiplying power, at 2.75~4.3V, 0.5C, discharge capacity is 162.4mAh/g, circulation for the first time
After 100 circles, capacity 148.2mAh/g, capacity retention ratio is up to 91.2%.
Respectively under the multiplying power of 0.2C, 0.5C, 1C, 2C, 5C, discharge capacity 168.7mAh/g, 162.1mAh/g,
148.1mAh/g、138.3mAh/g、120.4mAh/g。
Comparative example 1
With nickel-cobalt-manganternary ternary anode material Li (Ni0.6Co0.2Mn0.2)O2It is assembled as anode.
The assembling of battery: weighing 0.45g nickel-cobalt-manganternary ternary anode material, be added 0.025g conductive carbon black make conductive agent and
0.025g PVDF (Kynoar) makees binder, is coated on aluminium foil positive plate is made after mixing, in vacuum glove box
It is diaphragm with Celgard 2300 using metal lithium sheet as cathode, 1mol/L LiPF 6/EC:DMC (volume ratio 1:1) is electrolysis
Liquid is assembled into the button cell of CR2025.The battery assembled is in 2.5~4.3V voltage range, under 0.5C multiplying power, 2.75
Under~4.3V, 0.5C, discharge capacity is 165.7mAh/g for the first time, and after circulation 100 is enclosed, capacity 141.5mAh/g, capacity is kept
Rate is only 85.4%.
Respectively under the multiplying power of 0.2C, 0.5C, 1C, 2C, 5C, discharge capacity 169.3mAh/g, 158.3mAh/g,
143.8mAh/g、129.3mAh/g、104.3mAh/g。
The double oxide of the ternary material uncoated compared to comparative example 1, embodiment 1-4 preparation coats nickel-cobalt-manganese ternary material
Material is assembled into button cell, and circulation and high rate performance are promoted.The preparation method process of double oxide cladding is simple, at
This is cheap, is suitable for industrialized production.
The above statement is only preferred embodiment of the invention, it is noted that those skilled in the art, not
Under the premise of being detached from the invention design, various modifications and improvements can be made, these also should be regarded as protection of the invention
Within the scope of.
Claims (10)
1. a kind of preparation method of double oxide cladding tertiary cathode material, which comprises the following steps:
(1) tertiary cathode material is added in organic solvent, ultrasonic disperse obtains the first dispersion liquid；
(2) titanium source and silicon source are added to step (1) identical organic solvent, ultrasonic disperse obtains the second dispersion liquid；
(3) the first dispersion liquid and the second dispersion liquid are uniformly mixed, deionization is added dropwise according to the stoichiometric ratio of coating layer material
Water is stirred to react, then is evaporated all solvents, obtains composite material precursor；
(4) composite material precursor, which is calcined, is made double oxide cladding tertiary cathode material.
2. preparation method as described in claim 1, which is characterized in that in step (1), the tertiary cathode material is nickel cobalt
Manganese tertiary cathode material, chemical molecular formula are Li (Ni1-x-yCoxMny)O2, wherein 0 < x < 0.4,0 < y < 1.
3. preparation method as claimed in claim 1 or 2, which is characterized in that the tertiary cathode material partial size is 5-15 μm.
4. preparation method as described in claim 1, which is characterized in that in step (2), the titanium source be butyl titanate,
One or more of isopropyl titanate, titanium tetrachloride.
5. preparation method as described in claim 1, which is characterized in that in step (2), the silicon source be ethyl orthosilicate,
One or more of hexamethyldisiloxane, APTES.
6. preparation method as described in claim 1, which is characterized in that in step (2), the titanium source in terms of titanium with it is described
Molar ratio of the silicon source in terms of silicon is 3:2-8.
7. preparation method as claimed in claim 6, which is characterized in that the mass ratio of tertiary cathode material and titanium source in terms of titanium is
100:1。
8. preparation method as described in claim 1, which is characterized in that in step (3), the condition being stirred to react: temperature
Degree is 50-120 DEG C, revolving speed 500-1000r/min, time 2-5h.
9. preparation method as described in claim 1, which is characterized in that in step (4), the condition of the calcining: with 1-10
DEG C/rate of min is warming up to 300-800 DEG C, reaction time 2-10h.
10. a kind of double oxide as made from claim 1-9 described in any item preparation methods coats tertiary cathode material,
It is characterized in that, including tertiary cathode material and clad, the clad is made of silica and titanium oxide, the mass ratio of the two
For 1:0.5-2, the clad with a thickness of 1-10nm.
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