CN107591532A - A kind of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material and preparation method thereof - Google Patents
A kind of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material and preparation method thereof, belong to anode material for lithium-ion batteries technical field.Aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material of the present invention, has core shell structure, kernel is nickle cobalt lithium manganate LiNixCoyMn(1‑x‑y)O2, wherein, 0.5≤x≤1.0,0≤y≤0.23；The shell of core shell structure includes inner casing and shell, and wherein inner casing is aluminum fluoride, and shell is silver.Aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material of the present invention, has excellent cycle performance and a high first charge-discharge efficiency, and security performance is splendid.
Description
Technical field
The present invention relates to a kind of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material and preparation method thereof, belong to lithium
Ion battery positive electrode technical field.
Background technology
At present, anode material for lithium-ion batteries is studied with widely used as cobalt acid lithium material, lithium manganate material, phosphorus
Sour iron lithium material, ternary material etc..It is expensive but cobalt is scarce resource in lithium cobaltate cathode material, have to environment necessarily
Pollution；Although lithium nickelate theoretical specific capacity is high, synthesis is difficult, the poor reproducibility of material；Although the raw material resource of LiMn2O4
It is abundant, it is cheap, but spinel lithium manganate capacity is low, and Jahn-Teller effects easily occur for crystal structure, and capacity attenuation is fast,
Poor circulation.The performance of comprehensive cobalt acid lithium, lithium nickelate and LiMn2O4, by tri- kinds of transition metals of Ni, Co and Mn
With reference to lithium nickel cobalt manganese oxide, i.e. cobalt nickel lithium manganate ternary material (NCM) is prepared again, i.e., nickle cobalt lithium manganate is ternary layered
Positive electrode, its chemical formula are LiNi1-x-yCoxMnyO2, including Ni-based ternary material, or nickelic ternary material (LiNi1-x-
yCoxMnyO2)(1-x-y≥0.5).Due to the cooperative effect of tri- kinds of elements of Ni, Co and Mn, LiCoO is combined2、LiNiO2With
LiMnO2The advantages of three kinds of anode material for lithium-ion batteries, its performance are better than any of the above one-component positive electrode, existed bright
Aobvious cooperative effect.In the system, the chemical property and physical property of material are with these three transition metal ratios
Change and it is different, have the characteristics that heat endurance is good, energy density is high, under high potential specific capacity height it is low with cost of material, recognized
To be one of most promising anode material for lithium-ion batteries.
Although lithium nickel cobalt manganese oxide tertiary cathode material have many advantages, such as it is above-mentioned, its also exist it is following lack
Fall into：1) change due to cation mixing effect and material surface micro-structural during initial charge, causes ternary material
First charge-discharge efficiency it is not high；2) lithium ion diffusion coefficient and electronic conductivity are low so that the high rate performance deviation of material；3)
In wide voltage range with organic bath strong side reaction can occur for ternary material, cause its side reaction more, influence
Its cycle performance.And it is the method for solving drawbacks described above to carry out coating modification to ternary material at present, presently mainly pass through list
Layer carbon coating is to improve the multiplying power of material, cycle performance.Application publication number is that CN 106450217A Chinese invention patent discloses
A kind of method of modifying of cobalt nickel lithium manganate ternary material, it is effective to solve mainly by carrying out carbon coating to ternary material
The problem of lithium nickelate during traditional ternary material carbon coating is reduced, realizes bag of the carbon-coating on ternary material surface
Cover；Carbon coating cobalt nickel lithium manganate ternary material improves first charge-discharge efficiency, improves the lithium ion diffusion coefficient and electricity of material
Electron conductivity, improves the chemical property of NCM materials, but it has conductance improve amplitude little, clad and electrolysis
The compatibility of liquid is general, causes its cycle performance to improve amplitude unobvious, while its security performance deviation.
Application publication number is that CN105958017A Chinese invention patent discloses a kind of aluminum fluoride cladding nickle cobalt lithium manganate
The preparation method of positive electrode, the nickle cobalt lithium manganate coated by aluminum fluoride made from this method, its cycle performance and fills first
Electric discharge coulombic efficiency improves, but poor covered effect, electric conductivity, cyclicity be present only with aluminum fluoride cladding
The defects of energy, first charge-discharge efficiency increase rate unobvious.
The content of the invention
It is double-deck it is an object of the invention to provide a kind of aluminum fluoride that cycle performance is excellent, first charge-discharge efficiency is high/silver
Coat nickel-cobalt lithium manganate cathode material.
Second object of the present invention is to provide a kind of above-mentioned aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material
Preparation method.
To achieve the above object, the technical scheme is that：
A kind of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material, has core shell structure, and the kernel is nickel cobalt manganese
Sour lithium LiNixCoyMn(1-x-y)O2, wherein, 0.5≤x≤1.0,0≤y≤0.23；The shell of the core shell structure is including inner casing and outside
Shell, the inner casing are aluminum fluoride, and the shell is silver.
The thickness of the inner casing is 0.1~1 μm.
The thickness of the shell is 0.1~1 μm.
The mass ratio of the kernel and shell is 50~100：1~10.
A kind of preparation method of above-mentioned aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material, comprises the following steps：
1) preparation of aluminum fluoride mixed liquor：
Aluminum fluoride and organic carbon source, water are mixed, obtain the aluminum fluoride mixed liquor that aluminum fluoride concentration is 5-20%；The fluorination
The mass ratio of aluminium and organic carbon source is 21~35：10~30；The organic carbon source is in glucose, starch, sucrose, phenolic resin
Any one；
2) coat：
By aluminum fluoride mixed liquor and nickle cobalt lithium manganate LiNixCoyMn(1-x-y)O2Filtered after mixing, in 800~900 DEG C of sintering
2~12h, obtain the LiNi of aluminum fluoride claddingxCoyMn(1-x-y)O2；The LiNi that the aluminum fluoride is coatedxCoyMn(1-x-y)O2It was placed in
In the silver nitrate solution of amount, mix and excessive ammonia and acetaldehyde are added under the conditions of 50~100 DEG C, filter, wash after hybrid reaction
Wash, produce.
Aluminum fluoride in step 1) is prepared by following steps：Aluminium hydroxide and hydrofluoric acid solution are reacted into 2h at 100 DEG C
After filter and produce.Gained aluminum fluoride and organic carbon source, water are mixed, obtain the aluminum fluoride mixed liquor that aluminum fluoride concentration is 5-20%.
Above-mentioned aluminium hydroxide, hydrofluoric acid, the mass ratio of organic carbon source are 70~80：15~25：10~30.
Above-mentioned aluminium hydroxide is aluminium hydrate powder.The particle diameter of the aluminium hydrate powder is 10~20 μm.
Aluminum fluoride mixed liquor and nickle cobalt lithium manganate LiNi in step 2)xCoyMn(1-x-y)O2The relation of amount be：Every 500~
1000mL aluminum fluorides mixed liquor correspondingly adds 500g LiNixCoyMn(1-x-y)O2。
The concentration of ammoniacal liquor is 10% in step 2).
Silver nitrate solution passes through the silver with acetaldehyde with excess of ammonia water reaction generation silver ammino solution, silver ammino solution in step 2)
Mirror reaction obtains elemental silver, is coated on the outer layer of aluminum fluoride.
Crush and produce after being washed in step 2).
The nickle cobalt lithium manganate LiNixCoyMn(1-x-y)O2It is made by the preparation method comprised the following steps：
Nickel salt, cobalt salt, manganese salt and water are mixed, obtain precursor mixed solution；Added into the precursor mixed solution
Aqueous slkali and potassium persulfate solution, filtering after hybrid reaction, washing, dry presoma；The presoma is mixed with lithium salts
400~600 DEG C of 1~3h of insulation are first warming up to afterwards, then are warming up to 850~950 DEG C of 1~3h of insulation, are produced；The nickel salt, cobalt salt,
Manganese salt, alkali, potassium peroxydisulfate material amount ratio be 15~18：2~4：1：5~50：1~10；The thing of the presoma and lithium salts
The amount ratio of matter is 1：1~1.2.
The mass fraction of the aqueous slkali is 5~10%.
The aqueous slkali refers to alkaline solution.
The alkali is any one in sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium acid carbonate.
The alkali refers to alkaline matter.
The mass fraction of the potassium persulfate solution is 10%.
The above-mentioned heating rate for being warming up to 400~600 DEG C is 5 DEG C/min.
The above-mentioned heating rate for being warming up to 850~950 DEG C is 1~10 DEG C/min.
Above-mentioned nickel salt is any one in nickel sulfate, nickel nitrate, nickel chloride.
Above-mentioned cobalt salt is any one in cobaltous sulfate, cobalt nitrate, cobalt chloride.
Above-mentioned manganese salt is any one in manganese sulfate, manganese nitrate, manganese chloride.
Above-mentioned lithium salts is lithium hydroxide or lithium carbonate.
Above-mentioned presoma is polished after being mixed with lithium salts to heat up again.
Aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material of the present invention, utilizes the aluminium bag being fluorinated in aluminium compound
The electric conductivity and security performance of its material can be improved by overlaying on surface, at the same fluorine have with compatibility of electrolyte it is high the characteristics of, carry
Its high cycle performance, aluminium heat dispersion is high, can improve the security performance of material.One layer of silver material is deposited in outermost layer simultaneously,
The conduction velocity of electronics under the conditions of its big multiplying power is improved, and reduces the Probability of its side reaction, its cycle performance is improved and dissipates
Hot property.
The preparation method of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material of the present invention is simple, feasible, by this
The positive electrode that method is prepared has excellent cycle performance and high first charge-discharge efficiency.
Brief description of the drawings
Fig. 1 is the SEM figures of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material of the gained of the embodiment of the present invention 1.
Embodiment
Embodiment 1
The aluminum fluoride of the present embodiment/silver-colored double-coating nickel-cobalt lithium manganate cathode material, has core shell structure, and wherein kernel is
Nickle cobalt lithium manganate LiNi0.6Co0.2Mn0.2O2；The shell of core shell structure includes inner casing and shell, and inner casing is aluminum fluoride, and shell is silver；
The thickness of inner casing is 0.1 μm, and the thickness of shell is 0.1 μm；The mass ratio of kernel and shell is 50：5.
The preparation method of the aluminum fluoride of the present embodiment/silver-colored double-coating nickel-cobalt lithium manganate cathode material, comprises the following steps：
1) nickle cobalt lithium manganate LiNi0.6Co0.2Mn0.2O2Preparation：
After 419.2g nickel sulfates, 84.3g cobaltous sulfates, 15.1g manganese sulfates are well mixed, add 1000ml deionized waters and stir
Mix uniformly, be prepared into precursor mixed solution；106g sodium carbonate is dissolved in 1325g deionized waters simultaneously, being configured to concentration is
8% aqueous slkali；By potassium persulfate oxidation agent solution that aqueous slkali and 270ml concentration are 10%, (27g potassium peroxydisulfates are dissolved in afterwards
In 270g redistilled waters) it is added drop-wise in precursor mixed solution, after stirring, coprecipitation reaction liquid is obtained, is filtered afterwards,
Washing, dry presoma；Presoma is weighed afterwards and carries out mixed grinding with lithium hydroxide, and is transferred in tube furnace and is carried out height
Temperature reaction, is first warming up to 500 DEG C by 5 DEG C/min of heating rate, is incubated 2h, is warming up to afterwards with 1 DEG C/min heating rate
900 DEG C of insulation 2h, obtain LiNi0.6Co0.2Mn0.2O2Ternary material；Wherein, the mol ratio of presoma and lithium hydroxide is 1：
1.1；
2) preparation of aluminum fluoride mixed liquor：
First the aluminium-hydroxide powder 78g that particle diameter is 15 μm is put into 20ml hydrofluoric acid solutions, and it is anti-at a temperature of 100 DEG C
2h is answered, is filtrated to get aluminum fluoride afterwards, aluminum fluoride and 20g glucose, 1180g redistilled waters are stirred, obtain concentration
For 10% aluminum fluoride mixed liquor；
3) coating modification
500g LiNi is added into 800ml aluminum fluoride mixed liquorsxCoyMn(1-x-y)O2Ternary material, stir laggard
Row filtering, then sinters 12h in 800 DEG C, obtains the LiNi of aluminum fluoride cladding0.6Co0.2Mn0.2O2；Afterwards by aluminum fluoride cladding
LiNi0.6Co0.2Mn0.2O2It is added in 800ml silver nitrate solutiones, after stirring, under the conditions of temperature is 80 DEG C, is added dropwise
1000ml concentration is 10% ammonia spirit and acetaldehyde solution with 100ml 30%, and after stirring 2h, filters, wash, crush
Obtain aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material.
Embodiment 2
The aluminum fluoride of the present embodiment/silver-colored double-coating nickel-cobalt lithium manganate cathode material, has core shell structure, and wherein kernel is
Nickle cobalt lithium manganate LiNi0.6Co0.2Mn0.2O2；The shell of core shell structure includes inner casing and shell, and inner casing is aluminum fluoride, and shell is silver；
The thickness of inner casing is 1 μm, and the thickness of shell is 1 μm, and the mass ratio of kernel and shell is 100:1.
The preparation method of the aluminum fluoride of the present embodiment/silver-colored double-coating nickel-cobalt lithium manganate cathode material, comprises the following steps：
1) nickle cobalt lithium manganate LiNi0.6Co0.2Mn0.2O2Preparation：
After 435g nickel nitrates, 58.2g cobalt nitrates, 17.9g manganese nitrates are well mixed, the stirring of 1000ml deionized waters is added
Uniformly, it is prepared into precursor mixed solution；42g sodium acid carbonates are dissolved in 840g deionized waters simultaneously, are configured to concentration as 5%
Aqueous slkali；By potassium persulfate oxidation agent solution that aqueous slkali and 270ml concentration are 10%, (27g potassium peroxydisulfates are dissolved in afterwards
In 270g redistilled waters) it is added drop-wise in precursor mixed solution, after stirring, coprecipitation reaction liquid is obtained, is filtered afterwards,
Washing, is dried to obtain presoma；Presoma and lithium carbonate are subjected to mixed grinding, and it is anti-to be transferred to progress high temperature in tube furnace
Should, 400 DEG C first are warming up to by 5 DEG C/min of heating rate, 3h is incubated, is warming up to 850 DEG C afterwards with 5 DEG C/min heating rate
3h is incubated, obtains LiNi0.6Co0.2Mn0.2O2The mol ratio of ternary material, wherein presoma and lithium carbonate is 1：1；
2) preparation of aluminum fluoride mixed liquor：
First the aluminium-hydroxide powder 70g that particle diameter is 10 μm is put into 15ml hydrofluoric acid solutions, and it is anti-at a temperature of 100 DEG C
2h is answered, is filtrated to get aluminum fluoride afterwards, aluminum fluoride is added and is mixed evenly with 10g phenolic resin, 950g redistilled waters, is obtained
To the aluminum fluoride mixed liquor that concentration is 10%；
3) coating modification
500g LiNi is added into 500ml aluminum fluoride mixed liquors0.6Co0.2Mn0.2O2Ternary material, stir laggard
Row filtering, 2h sintering is then sintered in 900 DEG C, obtains the LiNi of aluminum fluoride cladding0.6Co0.2Mn0.2O2；Afterwards by aluminum fluoride bag
The LiNi covered0.6Co0.2Mn0.2O2It is added in 800ml silver nitrate solutiones, after stirring, under the conditions of temperature is 50 DEG C, drop
Add acetaldehyde solution of the 1000ml concentration for 10% ammonia spirit and 100ml 30%, and after stirring 2h, filter, washing, crush
To aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material.
Embodiment 3
The aluminum fluoride of the present embodiment/silver-colored double-coating nickel-cobalt lithium manganate cathode material, has core shell structure, and wherein kernel is
Nickle cobalt lithium manganate LiNi0.8Co0.1Mn0.1O2；The shell of core shell structure includes inner casing and shell, and inner casing is aluminum fluoride, and shell is silver；
The thickness of inner casing is 0.5 μm, and the thickness of shell is 0.5 μm, and the mass ratio of kernel and shell is 50:1.
The preparation method of the aluminum fluoride of the present embodiment/silver-colored double-coating nickel-cobalt lithium manganate cathode material, comprises the following steps：
1) nickle cobalt lithium manganate LiNi0.8Co0.1Mn0.1O2Preparation：
After 232.2g nickel chlorides, 51.6g cobalt chlorides, 12.6g manganese chlorides are well mixed, add 1000ml deionized waters and stir
Mix uniformly, be prepared into precursor mixed solution；420g sodium acid carbonates are dissolved in 4200g deionized waters simultaneously, are configured to concentration
For 10% aqueous slkali；Afterwards by potassium persulfate oxidation agent solution (270g persulfuric acid that aqueous slkali and 2700ml concentration are 10%
Potassium is dissolved in 2700g redistilled waters) it is added drop-wise in precursor mixed solution, after stirring, coprecipitation reaction liquid is obtained, it
After filter, wash, be dried to obtain presoma；Presoma and lithium hydroxide are subjected to mixed grinding, and are transferred in tube furnace
Row pyroreaction, 600 DEG C first are warming up to by 5 DEG C/min of heating rate, 1h are incubated, afterwards with 10 DEG C/min heating rate liter
Temperature obtains LiNi to 950 DEG C of insulation 1h0.8Co0.1Mn0.1O2Ternary material；Wherein, the mol ratio 1 of presoma and lithium hydroxide：
1.2；
2) preparation of aluminum fluoride mixed liquor：
First the aluminium-hydroxide powder 80g that particle diameter is 20 μm is put into 25ml hydrofluoric acid solutions, and it is anti-at a temperature of 100 DEG C
2h is answered, is filtrated to get aluminum fluoride afterwards, aluminum fluoride and 30g sucrose, 1350g redistilled waters are mixed evenly, obtained dense
Spend the aluminum fluoride mixed liquor for 10%；
3) coating modification
500g LiNi is added into 1000ml aluminum fluoride mixed liquors0.8Co0.1Mn0.1O2Ternary material, stir laggard
Row filtering, then sinters 8h in 850 DEG C, obtains the LiNi of aluminum fluoride cladding0.8Co0.1Mn0.1O2；Afterwards by aluminum fluoride cladding
LiNi0.8Co0.1Mn0.1O2It is added in 1500ml silver nitrate solutiones, after stirring, under the conditions of temperature is 100 DEG C, is added dropwise
2000ml concentration is 10% ammonia spirit and 100ml 50% acetaldehyde solution, and after stirring 2h, is filtered, and washing, is crushed
To aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material.
Comparative example
The LiNi for differing only in obtain aluminum fluoride cladding of this comparative example and embodiment 10.6Co0.2Mn0.2O2, no
Carry out silver-colored cladding.
Experimental example 1
SEM tests are carried out to aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material of gained in embodiment 1, as a result
As shown in figure 1, aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material of the gained of embodiment 1 is in uniform spherical, distribution conjunction
Reason.
Experimental example 2
Electrochemical property test：
1. make button cell test.
Button cell is dressed up as follows to the positive electrode that embodiment 1-3 and comparative example are prepared and tested：
1.1 add in 220mLN- methyl pyrrolidones in 95g positive electrodes, 1g Kynoar, 4g conductive agents SP,
Stir and prepare anode sizing agent, coated on copper foil, drying, roll pressing obtains positive pole.
Electrolyte uses LiPF6For electrolyte, concentration 1.3mol/L, volume ratio 1:1 EC and DEC is solvent, gold
Category lithium piece is used as to be used polyethylene (PE), polypropylene (PP) or poly- second propylene (PEP) composite membrane, is being flushed with hydrogen gas to electrode, barrier film
Glove box according to existing method assemble button cell A1, A2, A3 and B1.A1, A2, A3 and B1 be followed successively by using embodiment 1,
The battery that embodiment 2, embodiment 3, the positive electrode obtained by comparative example are assembled.
1.2 test above-mentioned button cell on new prestige 5V/10mA type cell testers, charging/discharging voltage scope 2.7-
4.2V, charge-discharge magnification 0.1C, test result are as shown in table 1.
The button cell test result of table 1
| Detain battery | A1 | A2 | A3 | B1 |
| Discharge capacity (mAh/g) first | 179.9 | 178.1 | 176.3 | 165.1 |
| Efficiency (%) first | 96.1 | 96.0 | 95.8 | 93.1 |
As can be seen from Table 1, the aluminum fluoride that embodiment 1-3 is prepared/silver-colored double-coating nickel-cobalt lithium manganate cathode material
Gram volume and its first efficiency are better than comparative example, the reason for this is that the fluorine atom adulterated in material, the gram volume for improving its material is sent out
Wave, while in its surface coated silver material, improve the transfer rate of lithium ion during its first charge-discharge, and it is first to improve its
Secondary efficiency.
2. soft-package battery is tested
Prepared respectively with embodiment 1, embodiment 2, the material that embodiment 3 and comparative example are prepared as positive electrode
Go out anode pole piece, using Delanium as negative material, using LiPF6/ EC+DEC (volume ratio 1: 1) is electrolyte, Celgard
2400 films are barrier film, prepare 5Ah soft-package battery C1, C2, C3 and D1, and test the cycle performance of its soft-package battery and forthright again
It is positive electrode that energy, wherein C1, C2, C3 and D1, which are followed successively by using embodiment 1, embodiment 2, embodiment 3, comparative example resulting materials,
The soft-package battery assembled.
2.1 high rate performance
Charged afterwards by 0.3C of multiplying power, the multiplying power using multiplying power as 1.0C, 2.0C, 3.0C, 4.0C is put respectively
Electricity, test voltage scope are 2.7V-4.2V, calculate discharge capacity and discharge capacitance afterwards.
The embodiment 1-3 of table 2 and the positive electrode of comparative example high rate performance
As can be seen from Table 2, using the soft-package battery of composite assembling obtained by embodiment 1-3 under the conditions of different multiplying
Multiplying power discharging ability be better than comparative example, the reason for this is that the positive electrode obtained by embodiment 1-3 is coated with the high silver-colored material of conductance
Material, improves the transmission rate of lithium ion and its electronics under the conditions of its big multiplying power, so as to improve its high rate performance.
2.2 security performances are tested：
Striking experiment：
Example 1-3 and each 10 of comparative example soft-package battery, it is after fully charged, the hard rod of a 16.0mm diameter is horizontal
It is put on battery, is fallen down and pounded on hard rod from 610mm height with one 20 pounds of weight, observes cell condition.
The striking experiment test result of table 3
| Project | Whether leakage | Whether catch fire |
| Embodiment 1 | It is no | It is no |
| Embodiment 2 | It is no | It is no |
| Embodiment 3 | It is no | It is no |
| Comparative example | It is | It is |
As can be seen from Table 3, the lithium ion battery prepared using embodiment 1-3 resulting materials is bright in terms of striking experiment
Show due to comparative example, the reason for this is that the aluminium in aluminum fluoride has the security that heat dispersion is high, improves its ternary material, therefore lithium
Security performance of the ion battery in terms of striking experiment is improved.
Claims (9)
1. a kind of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material, there is core shell structure, it is characterised in that in described
Core is nickle cobalt lithium manganate LiNixCoyMn(1-x-y)O2, wherein, 0.5≤x≤1.0,0≤y≤0.23；The shell bag of the core shell structure
Inner casing and shell are included, the inner casing is aluminum fluoride, and the shell is silver.
2. aluminum fluoride according to claim 1/silver-colored double-coating nickel-cobalt lithium manganate cathode material, it is characterised in that described
The thickness of inner casing is 0.1~1 μm.
3. aluminum fluoride according to claim 1/silver-colored double-coating nickel-cobalt lithium manganate cathode material, it is characterised in that described
The thickness of shell is 0.1~1 μm.
4. aluminum fluoride according to claim 1/silver-colored double-coating nickel-cobalt lithium manganate cathode material, it is characterised in that described
The mass ratio of kernel and shell is 50~100：1~10.
5. a kind of preparation method of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material as claimed in claim 1, it is special
Sign is, comprises the following steps：
1) preparation of aluminum fluoride mixed liquor：
Aluminum fluoride and organic carbon source, water are mixed, obtain the aluminum fluoride mixed liquor that aluminum fluoride concentration is 5-20%；The aluminum fluoride with
The mass ratio of organic carbon source is 21~35：10~30；The organic carbon source is appointing in glucose, starch, sucrose, phenolic resin
Meaning is a kind of；
2) coat：
By aluminum fluoride mixed liquor and nickle cobalt lithium manganate LiNixCoyMn(1-x-y)O2Filtered after mixing, in 800~900 DEG C sinter 2~
12h, obtain the LiNi of aluminum fluoride claddingxCoyMn(1-x-y)O2；The LiNi that the aluminum fluoride is coatedxCoyMn(1-x-y)O2It is placed in excess
Silver nitrate solution in, mix and excessive ammonia and acetaldehyde added under the conditions of 50~100 DEG C, filtering, washing after hybrid reaction,
Produce.
6. the preparation method of aluminum fluoride according to claim 5/silver-colored double-coating nickel-cobalt lithium manganate cathode material, its feature
It is, the nickle cobalt lithium manganate LiNixCoyMn(1-x-y)O2It is made by the preparation method comprised the following steps：
Nickel salt, cobalt salt, manganese salt and water are mixed, obtain precursor mixed solution；Alkali soluble is added into the precursor mixed solution
Liquid and potassium persulfate solution, filtering after hybrid reaction, washing, dry presoma；After the presoma is mixed with lithium salts first
400~600 DEG C of 1~3h of insulation are warming up to, then are warming up to 850~950 DEG C of 1~3h of insulation, are produced；The nickel salt, cobalt salt, manganese
Salt, alkali, potassium peroxydisulfate material amount ratio be 15~18：2~4：1：5~50：1~10；The material of the presoma and lithium salts
Amount ratio be 1：1~1.2.
7. the preparation method of aluminum fluoride according to claim 6/silver-colored double-coating nickel-cobalt lithium manganate cathode material, its feature
It is, the alkali is any one in sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium acid carbonate.
8. the preparation method of aluminum fluoride according to claim 6/silver-colored double-coating nickel-cobalt lithium manganate cathode material, its feature
It is, the heating rate for being warming up to 400~600 DEG C is 5 DEG C/min.
9. the preparation method of aluminum fluoride according to claim 6/silver-colored double-coating nickel-cobalt lithium manganate cathode material, its feature
It is, the heating rate for being warming up to 850~950 DEG C is 1~10 DEG C/min.
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