CN108847477A - A kind of nickle cobalt lithium manganate tertiary cathode material and preparation method thereof - Google Patents
A kind of nickle cobalt lithium manganate tertiary cathode material and preparation method thereof Download PDFInfo
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Abstract
High-performance cobalt nickel lithium manganate tertiary cathode material of doping vario-property and preparation method thereof is covered in a kind of double-contracting, and material includes Li (NiaCobMnc)1‑xMxO2With the two-coat for being attached to its surface；The two-coat inner layer is RyO, outer layer Al2O3；The lithium, nickel, cobalt, manganese, doped chemical M molar ratio be 1.02~1.12:a:b:c：0~0.12, wherein a >=0.5, a+b+c=1；The present invention is by being attached to Li (NiaCobMnc)1‑xMxO2The two-coat on surface improves high rate performance and cycle performance in electrical property；Preparation method covers the preparation of sample for the Ti doping synthesis of nickel-cobalt-manganese ternary material precursor, the preparation of Ti doped samples, double-contracting；Material energy densities of the present invention are high, and high rate performance is good, while the advantages of significantly improve the normal-temperature circulating performance of battery.
Description
Technical field
The present invention relates to technical field of lithium ion, in particular to a kind of nickle cobalt lithium manganate tertiary cathode material and its system
Preparation Method.
Background technique
Ternary cathode material of lithium ion battery (NCM) is since being found, just because of its capacity (theoretical capacity with higher
Up to 270mAh/g), excellent security performance, the factors such as cheap price advantage and obtained the extensive concern of researcher.So
And nickel-cobalt-manganese ternary material is in the prevalence of following problem：1. cation easily causes lithium to be precipitated in mixing；2. forthright again
Can be slightly worse compared with materials such as cobalt acid lithiums, cycle performance has to be hoisted；3. it is with electrolyte, compatibility is poor etc..These are solved at present to ask
The main method of topic is doping vario-property and surface cladding.And merely with doping to nickel-cobalt-manganese ternary material be modified there is
Certain defect, first is that inert matter element doping will lead to battery capacity loss, second is that battery is living in charge and discharge process
Property particle and electrolyte contacts, surface occurs oxide erosion, transition metal ions caused to dissolve, and forming surface texture collapses,
Cycle performance is deteriorated, and does not solve the problems, such as fundamentally to match with electrolyte.And it coats merely with surface to nickel cobalt manganese three
Although first material is modified the dissolution that metal ion can be effectively relieved, corrosion of the HF to active material is reduced, battery is improved
Cycle performance, but to the no any effect of the promotion of battery capacity.In this regard, how to play both doping vario-property and surface cladding
Synergistic effect, make using after nickel-cobalt-manganese ternary material while promoting battery energy density, but also with excellent forthright again
It can be the hot issue of current lithium electricity industry positive electrode research with good cycle performance.Therefore, how to select effectively to mix
Miscellaneous and covering material prepares the nickel-cobalt-manganese ternary material of function admirable, becomes and solves the problems, such as the above various bottleneck.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of nickle cobalt lithium manganate tertiary cathodes
Material and its preparation method, can produce with high capacity, high circulation conservation rate, the good nickel-cobalt-manganese ternary material of high rate performance
Material.
To achieve the goals above, the technical scheme is that：
A kind of nickle cobalt lithium manganate tertiary cathode material, including Li (NiaCobMnc)1-xMxO2With the double-contracting for being attached to its surface
Coating；The two-coat inner layer is RyO, outer layer Al2O3；The molar ratio of the lithium, nickel, cobalt, manganese, doped chemical M
It is 1.02~1.12:a:b:c：0~0.12, wherein a >=0.5, a+b+c=1.
The inner layer R of the cladyO accounts for Li (Ni with a thickness of 0.01-50nm, clad inner layeraCobMnc)1-xMxO2With
It is attached to the 0.01%~10% of the two-coat total mass fraction on its surface, preferably 0.05%~5%.
The inner layer R of the cladyO is WO3、Y2O3、La2O3One of.
The outer layer Al of the clad2O3With a thickness of 20-100nm, clad outer layer accounts for Li (NiaCobMnc)1-xMxO2
Total mass fraction with the two-coat for being attached to its surface is 0.05%~15%, preferably 0.1%~10%.
The doped chemical M is one of Ti, Cr.
The preparation method of the high-performance cobalt nickel lithium manganate tertiary cathode material of doping vario-property, step are covered in a kind of double-contracting：
Step 1：The synthesis of M doping nickel-cobalt-manganese ternary material precursor
By n (Ni)：n(Co)：n(Mn)：N (M)=a:b:c:The amount of 0~0.12 substance weighs its oxysalt, wherein a
Deionized water is added in >=0.5, a+b+c=1, and wherein oxysalt and the mass ratio of deionized water are 1：(1~6) is configured to molten
It is stirred 0.5~2 hour after liquid in 60~80 DEG C of heating water baths, the Na that concentration is 0.5~2mol/L is added2CO3Solution 0.2~
2L, while it is small to be aged 12~25 to control pH value of solution between 8~12 after reacting abundant for the ammonium hydroxide for instilling 0.1~2mol/L
When, after being filtered by vacuum, being washed, puts the precipitate in be dried in vacuo 4~8 hours in 100~120 DEG C of baking ovens and be mixed to get to M
Miscellaneous nickel-cobalt-manganese ternary material precursor；
Step 2：The preparation of M doped samples
The presoma and LiOH that step 1 is obtained are by the mass ratio of the material 1.02~1.12:1 mixing and ball milling, are collected
And divide double sintering in Muffle furnace：First stage is the pre-burning stage, rises to 350~550 DEG C from room temperature, is sintered 6 in air
~10 hours；Second stage is the solid phase reaction stage, is warming up to 800~980 DEG C, is sintered 8~12 hours in oxygen atmosphere, with
Furnace is cooled to room temperature, and is to obtain M doped samples after being crushed, crossing 300 meshes；
Step 3：The preparation of sample is covered in double-contracting：
Dry preparation process process：
By in the M doped samples in step 2 with metal oxide nano powder according to molar ratio (0~0.12)：(0.01
~0.15) it, is put into ball grinder and mixes, 300~1000r/min of revolving speed, grinding 4~8 hours, then again by obtained powder
It is calcined, rises to 450~750 DEG C from room temperature, be sintered 8~10 hours in air, cool to room temperature with the furnace, through broken, mistake
Cladding sample one is obtained after sieve；
Cladding sample one is add to deionized water, and lithium source is added, covers sample one：Ionized water：The mass ratio of lithium source
It is 1：50~200：1.02~1.12, obtain mixed liquor A；Silicon source is added to deionized water, the addition of silicon source and deionized water
Ratio is volume ratio 0.1~1.2:10, it is stirred well to and is completely dissolved using magnetic stirring apparatus, generated after being mixed with mixed liquor A
Sediment, mixed volume ratio 1:1, sediment is crossed into 300 mesh after filtering, drying, 450~650 DEG C are calcined 4~6 hours
Sieve, obtains the high-performance cobalt nickel lithium manganate tertiary cathode material that doping vario-property is covered in double-contracting.
Wet method preparation process process：
RCl is prepared with hydrochloridey, configuration concentration is 0.5~2mol/L, after 0.035~0.42g/mL dispersing agent is added,
The M doped samples in step 2 are added, ultrasonic disperse is uniform, and the hydrochloride prepares RCly, dispersing agent, M doped samples
Mass ratio is (0.1~0.15)：(2~6)：(80~200)；It is the heavy of 0.5~2mol/L that concentration is added dropwise under magnetic agitation
Agent sodium carbonate in shallow lake generates sediment and filters out, is washed with deionized water；60~120 DEG C of drying, then again by obtained powder
It is secondary to be calcined, 450~750 DEG C are risen to from room temperature, is sintered 8~10 hours in air, cools to room temperature with the furnace, be crushed,
It crosses after 300 meshes and obtains cladding sample one；
Cladding sample one is added in deionized water, lithium source is added, coats sample one：Ionized water：Lithium source mass ratio is 1：
50~200：1.02~1.12, obtain mixed liquor A；Silicon source is add to deionized water, the addition ratio of silicon source and deionized water
Example is volume ratio 0.1~1.2:10, it is stirred well to and is completely dissolved using magnetic stirring apparatus, it is heavy to generate after mixing with mixed liquor A
Starch, mixed proportion 1:1, sediment is crossed into 300 meshes after filtering, drying, 450~650 DEG C are calcined 4~6 hours, is obtained
The high-performance cobalt nickel lithium manganate tertiary cathode material of doping vario-property is covered to double-contracting.
The oxysalt is sulfate, acetate, two or three in nitrate.
The metal oxide nano powder is WO3、Y2O3、La2O3One of.
The dispersing agent is polyvinylpyrrolidone.
Beneficial effects of the present invention：
The present invention is by being attached to Li (NiaCobMnc)1-xMxO2The two-coat on surface improves forthright again in electrical property
Energy and cycle performance；M metal ion have a variety of valence states, mix matrix after in charge and discharge process with Ni2+It is oxidized simultaneously, it can
Higher first charge-discharge specific capacity is obtained, and allows to be large current discharge.Nanomorphic RyO has good dielectric properties, energy
Enough obvious division (006)/(012) and (018)/(110) are bimodal, form more perfect layer structure, improve the multiplying power of material
Performance；And the Al of external sheath2O3Protective film can be formed, corrosion of the electrolyte to basis material is reduced, so as to improve material
Cycle performance.Using the height of material energy densities prepared by the method, high rate performance is good, while significantly improving the normal of battery
Warm cycle performance.
Specific embodiment
Below with reference to example, WO is coated with bulk phase-doped Ti, inner layer3, external sheath Al2O3For, be respectively adopted dry method and
Wet processing prepares NCM523, NCM622, NCM811.
Embodiment one
The preparation method of the high-performance cobalt nickel lithium manganate tertiary cathode material of doping vario-property, step are covered in a kind of double-contracting：
Step 1：The synthesis of Ti doping nickel-cobalt-manganese ternary material precursor：
Using nickel sulfate, cobalt acetate, manganese acetate, M sulfate as raw material, by n (Ni)： n(Co)：n(Mn)：N (Ti)=
0.5:0.2:0.3:Nickel sulfate, the 0.19mol cobalt acetate, 0.285mol second of 0.08 the mass ratio of the material precise 0.475mol
Sour manganese, 0.076mol titanium sulfate be placed in a beaker, stirred after being configured to solution with 25mL deionized water in 80 DEG C of heating water baths
2 hours, the Na of 1.0mol/L is added2CO3Solution mixing 0.2L, at the same instill the ammonium hydroxide of 1.5mol/L with control pH value of solution 9~
It between 10, is aged 20 hours after reacting sufficiently, after being filtered by vacuum, being washed, it is dry to put the precipitate in vacuum in 100 DEG C of baking ovens
Nickel-cobalt-manganese ternary material precursor is adulterated to get to Ti within dry 4 hours；
Step 2：The preparation of Ti doped samples：
Ti obtained in step 1 is adulterated into nickel-cobalt-manganese ternary material precursor and LiOH presses the mass ratio of the material 1.08:1 is mixed
Merge ball milling, preferably carry out in a planetary ball mill, revolving speed 1000r/min, grinds 2 hours；It is collected after grinding uniformly
And divide double sintering in Muffle furnace：First stage is the pre-burning stage, rises to 550 DEG C from room temperature, is sintered 6 hours in air；
Second stage is the solid phase reaction stage, is warming up to 920 DEG C, is sintered 12 hours in oxygen atmosphere, cools to room temperature with the furnace, through broken
Ti doped samples are obtained after broken, 300 meshes excessively；
Step 3：The preparation of sample is covered in double-contracting：
Dry preparation process process：
WO will be added in Ti doped samples in step 23Nano powder, Ti doped samples and WO3The molar ratio of nano powder is
0.12:0.15, it is put into ball grinder and mixes, revolving speed 300r/min grinds 4 hours, then forges obtained powder again
It burns, rises to 650 DEG C from room temperature, be sintered 10 hours in air, cool to room temperature with the furnace, coated after broken, sieving
Sample one；
Sample one will be covered to be add to deionized water, and lithium source is added, cover sample one：Ionized water：The mass ratio of lithium source is
1：200：1.12, mixed liquor A is obtained, silicon source is add to deionized water, the additional proportion of silicon source and deionized water is volume
Than 0.1:10, it is stirred well to and is completely dissolved using magnetic stirring apparatus, generate sediment after mixing with mixed liquor A, by sediment
300 meshes are crossed after filtering, drying, 450 DEG C are calcined 4 hours, obtain the cladding sample two, as final products.
Wet method preparation process process：
WCl is prepared with hydrochloride6, step is added in configuration concentration 1.0mol/L, addition 0.035g/mL dispersing agent PVP
Two obtained middle Ti doped samples, ultrasonic disperse is uniform, and the precipitating reagent that concentration is 0.5mol/L is added dropwise under magnetic agitation
Na2CO3, generate sediment and filter out, be washed with deionized water；100 DEG C of drying, then forge obtained powder again
It burns, rises to 650 DEG C from room temperature, be sintered 8 hours in air, cool to room temperature with the furnace, obtained after being crushed, crossing 300 meshes
Coat sample one；
Cladding sample one is add to deionized water, and lithium source is added, covers sample one：Ionized water：Lithium source mass ratio is
1：200：1.12, obtain mixed liquor A；Silicon source is add to deionized water, the additional proportion of silicon source and deionized water is volume
Than 0.1:10, it is stirred well to and is completely dissolved using magnetic stirring apparatus, generate sediment after mixing with mixed liquor A, by sediment
300 meshes are crossed after filtering, drying, 450 DEG C are calcined 4 hours, obtain the cladding sample two, as final products.
Embodiment two
The preparation method of the high-performance cobalt nickel lithium manganate tertiary cathode material of doping vario-property, step are covered in a kind of double-contracting：
Step 1：The synthesis of Ti doping nickel-cobalt-manganese ternary material precursor：
Using nickel sulfate, cobalt acetate, manganese acetate, titanium sulfate as raw material, by n (Ni)：n (Co)：n(Mn)：N (Ti)=0.6:
0.2:0.2:The nickel sulfate of 0.08 the mass ratio of the material precise 0.57mol, 0.19mol cobalt acetate, 0.19mol manganese acetate,
The titanium sulfate of 0.076mol is placed in a beaker, small in 80 DEG C of heating water bath stirrings 2 after being configured to solution with deionized water 100mL
When, with 0.2L, the Na of 1.0mol/L2CO3Solution mixing, while instill the ammonium hydroxide of 1.5mol/L with control pH value of solution 9~10 it
Between, it is aged 20 hours after reacting sufficiently, after being filtered by vacuum, being washed, puts the precipitate in 100 DEG C of baking ovens and be dried in vacuo 4
Hour adulterates nickel-cobalt-manganese ternary material precursor to get to Ti；
Step 2：The preparation of Ti doped samples
Ti obtained in step 1 is adulterated into nickel-cobalt-manganese ternary material precursor and LiOH presses the mass ratio of the material 1.08:1 is mixed
Merge ball milling, preferably carry out in a planetary ball mill, revolving speed 800r/min, grinds 4 hours；Grind uniform collection and
Divide double sintering in Muffle furnace：First stage is the pre-burning stage, rises to 450 DEG C from room temperature, is sintered 6 hours in air；Second
Stage is the solid phase reaction stage, is warming up to 870 DEG C, is sintered 12 hours in oxygen atmosphere, cools to room temperature with the furnace, be crushed,
It crosses and obtains Ti doped samples after 300 meshes；
Step 3：The preparation of sample is covered in double-contracting：
Dry preparation process process：
WO will be added in Ti doped samples obtained in step 23Nano powder, molar ratio 0.10：0.08, it is put into
It is mixed in ball grinder, revolving speed 300r/min, grinds 4 hours, obtained powder is calcined again then, is risen to from room temperature
It 650 DEG C, is sintered 10 hours in air, cools to room temperature with the furnace, cladding sample one is obtained after broken, sieving；
Obtained cladding sample one is add to deionized water, and lithium source is added, covers sample one：Ionized water：Lithium source
Mass ratio be 1：50：1.02, mixed liquor A is obtained, silicon source is add to deionized water, the addition ratio of silicon source and deionized water
Example is volume ratio 0.1:10, it is stirred well to and is completely dissolved using magnetic stirring apparatus, generate sediment after mixing with mixed liquor A,
Sediment is crossed into 300 meshes after filtering, drying, 450 DEG C are calcined 4 hours, obtains the cladding sample two, it is as final to produce
Product.
Wet method preparation process process：
WCl is prepared with hydrochloride6, configuration concentration 1.0mol/L, addition dispersing agent PVP are added step 2 Ti and adulterate sample
Product, ultrasonic disperse is uniform, and the hydrochloride prepares WCl6, dispersing agent PVP, M doped samples mass ratio be 0.1：2：80 magnetic
The precipitating reagent Na that concentration is 0.5mol/L is added dropwise under power stirring2CO3, generate sediment and filter out, be washed with deionized water
Only；100 DEG C of drying, then obtained powder is calcined, rise to 650 DEG C from room temperature again, is sintered 8 hours in air,
It cools to room temperature with the furnace, cladding sample one is obtained after being crushed, crossing 300 meshes.
Cladding sample one is add to deionized water, and lithium source is added, obtains mixed liquor A, coats sample one：Ion
Water：Lithium source mass ratio is 1：200：1.10, silicon source is add to deionized water, the additional proportion of silicon source and deionized water is body
Product ratio 0.1~1.2, is stirred well to using magnetic stirring apparatus and is completely dissolved, generate sediment after mixing with mixed liquor A, will sunk
Starch crosses 300 meshes after filtering, drying, 450 DEG C are calcined 4 hours, obtains the cladding sample two, as final products.
Embodiment three
A kind of preparation method for the high-performance cobalt nickel lithium manganate tertiary cathode material that coating-doping is modified, including following step
Suddenly：
Step 1：The synthesis of Ti doping nickel-cobalt-manganese ternary material precursor：
Using nickel sulfate, cobalt acetate, manganese acetate, M sulfate as raw material, by n (Ni)： n(Co)：n(Mn)；N (Ti)=
0.8:0.1:0.1:Nickel sulfate, the 0.095mol cobalt acetate, 0.095mol second of 0.08 the mass ratio of the material precise 0.76mol
Sour manganese, 0.076mol titanium sulfate be placed in a beaker, be added deionization 150mL water be configured to after solution in 80 DEG C of heating water baths
Stirring 2 hours, with 0.2L, the Na of 1mol/L2CO3Solution mixing, while the ammonium hydroxide of 1.5mol/L is instilled to control pH value of solution 9
Between~10, it is aged 20 hours after reacting sufficiently, after being filtered by vacuum, being washed, puts the precipitate in vacuum in 100 DEG C of baking ovens
Nickel-cobalt-manganese ternary material precursor is adulterated to get to Ti within dry 4 hours；
Step 2：The preparation of Ti doped samples
Ti obtained in step 1 is adulterated into nickel-cobalt-manganese ternary material precursor and LiOH presses the mass ratio of the material 1.08:1 is mixed
Merge ball milling, preferably carry out in a planetary ball mill, revolving speed 600r/min, grinds 6 hours；Grind uniform collection and
Divide double sintering in Muffle furnace：First stage is the pre-burning stage, rises to 350 DEG C from room temperature, is sintered 6 hours in air；Second
Stage is the solid phase reaction stage, is warming up to 800 DEG C, is sintered 12 hours in oxygen atmosphere, cools to room temperature with the furnace, be crushed,
It crosses and obtains Ti doped samples after 300 meshes；
Step 3：The preparation of sample is covered in double-contracting：
Dry preparation process process：
WO will be added in Ti doped samples obtained in step 23Nano powder, molar ratio 0.06：0.08, it is put into ball
It is mixed in grinding jar, revolving speed 300r/min, grinds 4 hours, obtained powder is calcined again then, rises to 650 from room temperature
DEG C, it is sintered 10 hours in air, cools to room temperature with the furnace, cladding sample one is obtained after broken, sieving；
Cladding sample one is add to deionized water, and lithium source is added, coats sample one：Ionized water：The quality of lithium source
Than being 1：200：1.12, obtain mixed liquor A；Silicon source is add to deionized water, the additional proportion of silicon source and deionized water is
Volume ratio 1.2:10, it is stirred well to and is completely dissolved using magnetic stirring apparatus, generate sediment after mixing with mixed liquor A, will sunk
Starch crosses 300 meshes after filtering, drying, 450 DEG C are calcined 4 hours, obtains the cladding sample two, as final products.
Wet method preparation process process：
WCl is prepared with hydrochloride6, step 2 is added in configuration concentration 1.0mol/L, addition 0.42g/mL dispersing agent PVP
In obtained Ti doped samples, the hydrochloride prepares WCl6, dispersing agent PVP, M doped samples mass ratio be 0.15：
6：200, ultrasonic disperse is uniform, and the precipitating reagent Na that concentration is 0.5mol/L is added dropwise under magnetic agitation2CO3, generate sediment
And filter out, it is washed with deionized water；100 DEG C of drying, then obtained powder is calcined, rise to 650 from room temperature again
DEG C, it is sintered 8 hours in air, cools to room temperature with the furnace, cladding sample one is obtained after being crushed, crossing 300 meshes；
Cladding sample one is add to deionized water, and lithium source is added, coats sample one：Ionized water：Lithium source mass ratio
It is 1：200：1.12, obtain mixed liquor A；Silicon source is add to deionized water, the additional proportion of silicon source and deionized water is body
Product ratio 1.2:10, it is stirred well to and is completely dissolved using magnetic stirring apparatus, generate sediment after mixing with mixed liquor A, will precipitated
Object crosses 300 meshes after filtering, drying, 450 DEG C are calcined 4 hours, obtains the cladding sample two, as final products.
Comparative example one
(1) synthesis of conventional nickel-cobalt-manganese ternary material precursor：
Using nickel sulfate, cobalt acetate, manganese acetate as raw material, by n (Ni)：n(Co)：N (Mn)=0.5:0.2:0.3 substance
Nickel sulfate of the amount than precise 0.475mol, 0.19mol cobalt acetate, 0.285mol manganese acetate be placed in a beaker, spend from
Sub- water 150mL is stirred 2 hours after being configured to solution in 80 DEG C of heating water baths, the Na with 1mol/L2CO3Solution 20ml mixing, together
When instill 1.0mol/L ammonium hydroxide to control pH value of solution between 9~10, wait react sufficiently after be aged 20 hours.It is taken out through vacuum
After filter, washing, puts the precipitate in 100 DEG C of baking ovens and be dried in vacuo 4 hours to get conventional nickel-cobalt-manganese ternary material precursor is arrived
Ni0.5Co0.2Mn0.3CO3；
(2) preparation of conventional nickel-cobalt-manganese ternary material：
Presoma obtained in step (1) and LiOH are pressed the mass ratio of the material 1.08 by step 1:Simultaneously ball milling is equal for 1 mixing
It is even, it preferably carries out, revolving speed 1000r/min, grinds 2 hours in a planetary ball mill；
Step 2 divides uniformly mixed material collection and in Muffle furnace double sintering：First stage is the pre-burning stage,
550 DEG C are risen to from room temperature, is sintered 6 hours in air；Second stage is the solid phase reaction stage, 920 DEG C is warming up to, in oxygen atmosphere
Middle sintering 12 hours is enclosed, cools to room temperature with the furnace, obtains conventional nickel-cobalt-manganese ternary material Li after broken, 300 mesh sieving
(Ni0.5Co0.2Mn0.3)O2。
Comparative example two
(1) synthesis of conventional nickel-cobalt-manganese ternary material precursor：
Using nickel sulfate, cobalt acetate, manganese acetate as raw material, by n (Ni)：n(Co)：N (Mn)=0.6:0.2:0.2 substance
Nickel sulfate of the amount than precise 0.57mol, 0.19mol cobalt acetate, 0.19mol manganese acetate be placed in a beaker, use deionization
Water 150mL is stirred 2 hours after being configured to solution in 80 DEG C of heating water baths, the Na with 1mol/L2CO3Solution 20ml mixing, simultaneously
The ammonium hydroxide of 1.0mol/L is instilled to control pH value of solution between 9~10, is aged 20 hours after reacting sufficiently.Be filtered by vacuum,
After washing, puts the precipitate in 100 DEG C of baking ovens and be dried in vacuo 4 hours to get conventional nickel-cobalt-manganese ternary material precursor is arrived
Ni0.6Co0.2Mn0.2CO3；
(2) preparation of conventional nickel-cobalt-manganese ternary material：
Step 1, by presoma and Li obtained in step (1)2OH presses the mass ratio of the material 1.08:Simultaneously ball milling is equal for 1 mixing
It is even, it preferably carries out, revolving speed 800r/min, grinds 4 hours in a planetary ball mill；
Step 2 divides uniformly mixed material collection and in Muffle furnace double sintering：First stage is the pre-burning stage,
550 DEG C are risen to from room temperature, is sintered 6 hours in air；Second stage is the solid phase reaction stage, 870 DEG C is warming up to, in oxygen atmosphere
Middle sintering 12 hours is enclosed, cools to room temperature with the furnace, obtains conventional nickel-cobalt-manganese ternary material Li after broken, 300 mesh sieving
(Ni0.6Co0.2Mn0.2)O2。
Comparative example three
(1) synthesis of conventional nickel-cobalt-manganese ternary material precursor：
Using nickel sulfate, cobalt acetate, manganese acetate as raw material, by n (Ni)：n(Co)：N (Mn)=0.8:0.1:0.1 substance
Nickel sulfate of the amount than precise 0.76mol, 0.095mol cobalt acetate, 0.095mol manganese acetate be placed in a beaker, spend from
Sub- water 150mL is stirred 2 hours after being configured to solution in 80 DEG C of heating water baths, the Na with 1mol/L2CO3Solution 20ml mixing, together
When instill 1.0mol/L ammonium hydroxide to control pH value of solution between 9~10, wait react sufficiently after be aged 20 hours.It is taken out through vacuum
After filter, washing, puts the precipitate in 100 DEG C of baking ovens and be dried in vacuo 4 hours to get conventional nickel-cobalt-manganese ternary material precursor is arrived
Ni0.8Co0.1Mn0.1CO3；
(2) preparation of conventional nickel-cobalt-manganese ternary material：
Presoma obtained in step (1) and LiOH are pressed the mass ratio of the material 1.08 by step 1:Simultaneously ball milling is equal for 1 mixing
It is even, it preferably carries out, revolving speed 600r/min, grinds 6 hours in a planetary ball mill.
Step 2 divides uniformly mixed material collection and in Muffle furnace double sintering：First stage is the pre-burning stage,
550 DEG C are risen to from room temperature, is sintered 6 hours in air；Second stage is the solid phase reaction stage, 800 DEG C is warming up to, in oxygen atmosphere
Middle sintering 12 hours is enclosed, cools to room temperature with the furnace, obtains conventional nickel-cobalt-manganese ternary material Li after broken, 300 mesh sieving
(Ni0.8Co0.1Mn0.1)O2。
It carries out 2025 button electricity production to above-described embodiment and comparative example to test, test voltage condition (3.0-4.3) V,
High rate performance test condition：The two circle charge and discharge of 0.2C, 0.5C, 1C, 2C, 5C difference, high rate performance calculation method：5C discharge capacity/
0.2C discharge capacity.
Table one gives comparative example 1~3 and the 0.1C head for buckleing electricity of Examples 1 to 3 ternary sample puts specific capacity, multiplying power
Performance and cycle performance data.
The 0.2C head of table one, comparative example and embodiment sample puts specific capacity, high rate performance and cycle performance
The result shows that by bulk phase-doped M, surface coats R simultaneouslyyO&Al2O3Ternary material afterwards it is relatively conventional (it is undoped,
It is uncoated) the 0.1C head of sample puts specific capacity and has and increase substantially；Meanwhile the electrical property of the ternary material after double coating-dopings
High rate performance and cycle performance in energy also have clear improvement.
Claims (9)
1. a kind of nickle cobalt lithium manganate tertiary cathode material, which is characterized in that including Li (NiaCobMnc)1-xMxO2Be attached to its table
The two-coat in face；The two-coat inner layer is RyO, outer layer Al2O3；The lithium, nickel, cobalt, manganese, doped chemical M
Molar ratio is 1.02~1.12:a:b:c：0~0.12, wherein a >=0.5, a+b+c=1.
2. a kind of nickle cobalt lithium manganate tertiary cathode material according to claim 1, which is characterized in that the clad
Inner layer RyO accounts for Li (Ni with a thickness of 0.01-50nm, clad inner layeraCobMnc)1-xMxO2With the two-coat for being attached to its surface
The 0.01%~10% of total mass fraction, preferably 0.05%~5%.
3. a kind of nickle cobalt lithium manganate tertiary cathode material according to claim 1, which is characterized in that the clad
Inner layer RyO is WO3、Y2O3、La2O3One of.
4. a kind of nickle cobalt lithium manganate tertiary cathode material according to claim 1, which is characterized in that the clad
Outer layer Al2O3With a thickness of 20-100nm, clad outer layer accounts for Li (NiaCobMnc)1-xMxO2It is covered with the double-contracting for being attached to its surface
The total mass fraction of layer is 0.05%~15%, preferably 0.1%~10%.
5. a kind of nickle cobalt lithium manganate tertiary cathode material according to claim 1, which is characterized in that the doped chemical
M is one of Ti, Cr.
6. the preparation method that the high-performance cobalt nickel lithium manganate tertiary cathode material of doping vario-property is covered in a kind of double-contracting, which is characterized in that
Its step：
Step 1：The synthesis of M doping nickel-cobalt-manganese ternary material precursor
By n (Ni)：n(Co)：n(Mn)：N (M)=a:b:c:The amount of 0~0.12 substance weighs its oxysalt, wherein a >=
0.5, a+b+c=1, deionized water is added, wherein oxysalt and the mass ratio of deionized water are 1：(1~6), is configured to solution
It is stirred 0.5~2 hour in 60~80 DEG C of heating water baths afterwards, the Na that concentration is 0.5~2mol/L is added2CO30.2~2L of solution, together
When instill 0.1~2mol/L ammonium hydroxide to control pH value of solution between 8~12, wait react sufficiently after be aged 12~25 hours, warp
After vacuum filtration, washing, puts the precipitate in 100~120 DEG C of baking ovens to be dried in vacuo 4~8 hours and adulterate nickel cobalt to get to M
Manganese ternary material precursor；
Step 2：The preparation of M doped samples
The presoma and LiOH that step 1 is obtained are by the mass ratio of the material 1.02~1.12:1 mixing and ball milling, collect and
Divide double sintering in Muffle furnace：First stage is the pre-burning stage, rises to 350~550 DEG C from room temperature, is sintered 6~10 in air
Hour；Second stage is the solid phase reaction stage, is warming up to 800~980 DEG C, is sintered 8~12 hours in oxygen atmosphere, cold with furnace
It but is to obtain M doped samples after being crushed, crossing 300 meshes to room temperature；
Step 3：The preparation of sample is covered in double-contracting：
Dry preparation process process：
By in the M doped samples in step 2 with metal oxide nano powder according to molar ratio (0~0.12)：(0.01~
0.15), be put into ball grinder and mix, 300~1000r/min of revolving speed, grind 4~8 hours, then by obtained powder again into
Row calcining, rises to 450~750 DEG C from room temperature, is sintered 8~10 hours in air, cools to room temperature with the furnace, through broken, sieving
Cladding sample one is obtained afterwards；
Cladding sample one is add to deionized water, and lithium source is added, covers sample one：Ionized water：The mass ratio of lithium source is 1：
50~200：1.02~1.12, obtain mixed liquor A；Silicon source is added to deionized water, the additional proportion of silicon source and deionized water
For volume ratio 0.1~1.2:10, it is stirred well to and is completely dissolved using magnetic stirring apparatus, precipitating is generated after mixing with mixed liquor A
Object, mixed volume ratio 1:1, sediment is crossed into 300 meshes after filtering, drying, 450~650 DEG C are calcined 4~6 hours, is obtained
The high-performance cobalt nickel lithium manganate tertiary cathode material of doping vario-property is covered in double-contracting.
Wet method preparation process process：
RCl is prepared with hydrochloridey, configuration concentration is 0.5~2mol/L, and after 0.035~0.42g/mL dispersing agent is added, step is added
M doped samples in rapid two, ultrasonic disperse is uniform, and the hydrochloride prepares RCly, dispersing agent, M doped samples mass ratio
For (0.1~0.15)：(2~6)：(80~200)；The precipitating reagent carbon that concentration is 0.5~2mol/L is added dropwise under magnetic agitation
Sour sodium generates sediment and filters out, is washed with deionized water；60~120 DEG C of drying, then carry out obtained powder again
Calcining, rises to 450~750 DEG C from room temperature, is sintered 8~10 hours in air, cools to room temperature with the furnace, is crushed, crosses 300 mesh
Cladding sample one is obtained after sieve；
Cladding sample one is added in deionized water, lithium source is added, coats sample one：Ionized water：Lithium source mass ratio is 1：50~
200：1.02~1.12, obtain mixed liquor A；Silicon source is add to deionized water, the additional proportion of silicon source and deionized water is
Volume ratio 0.1~1.2:10, it is stirred well to and is completely dissolved using magnetic stirring apparatus, generate sediment after mixing with mixed liquor A,
Mixed proportion is 1:1, sediment is crossed into 300 meshes after filtering, drying, 450~650 DEG C are calcined 4~6 hours, obtains double-contracting
Cover the high-performance cobalt nickel lithium manganate tertiary cathode material of doping vario-property.
7. a kind of preparation method of nickle cobalt lithium manganate tertiary cathode material according to claim 6, which is characterized in that described
Oxysalt be sulfate, acetate, two or three in nitrate.
8. a kind of preparation method of nickle cobalt lithium manganate tertiary cathode material according to claim 6, which is characterized in that described
Metal oxide nano powder be WO3、Y2O3、La2O3One of.
9. a kind of preparation method of nickle cobalt lithium manganate tertiary cathode material according to claim 6, which is characterized in that described
Dispersing agent be polyvinylpyrrolidone.
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