CN107528064A - A kind of high voltage type class monocrystalline tertiary cathode material and preparation method thereof - Google Patents
A kind of high voltage type class monocrystalline tertiary cathode material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention belongs to technical field of lithium ion battery electrode, discloses a kind of high voltage type class monocrystalline tertiary cathode material and preparation method thereof.Preparation method of the present invention comprises the following steps：By nickel salt, cobalt salt, manganese salt, ammoniacal liquor complexing agent and ammonium oxalate the precipitating reagent hybrid reaction in water, presoma is obtained；Mixed with lithium source, 100~400rpm ball millings, 3~6h；In atmosphere furnace, air or oxygen atmosphere, 1~10 DEG C is warming up to 450~750 DEG C, and 4~10h of sintering is down to normal temperature；400~750rpm ball mill grindings, 5~8h；Mixed with lithium source, 100~400rpm ball milling mixings, 1~4h；In atmosphere furnace, oxygen atmosphere, 3~10 DEG C/min is warming up to 450~600 DEG C, calcines 2~6h, and 1~5 DEG C/min is warming up to 750~950 DEG C of 8~12h of calcining and is down to room temperature, and high voltage type class monocrystalline tertiary cathode material is obtained through broken, crushing, sieving.
Description
Technical field
The invention belongs to technical field of lithium ion battery electrode, more particularly to a kind of high voltage type class monocrystalline ternary is just
Pole material and preparation method thereof.
Background technology
In recent years, lithium ion battery is long because having the advantages that, small volume higher than energy, light weight and cycle performance, not only
The portable electric appts such as notebook computer, digital camera, mobile device are widely used in, and are gradually applied to electricity
The powerful devices such as motor-car, hybrid electric vehicle, accumulation power supply.In order to meet the requirement of these powerful devices, high-energy-density,
The study hotspot for being developed into cell positive material of the good positive electrode of low cost, cycle of higher pressure stability.Nickle cobalt lithium manganate
(NCM) tertiary cathode material (LiNixCoyMn1-x-yO2, 0 ＜ x, y ＜ 1) and have that energy density is high, have a safety feature, cost is cheap
The advantages of, turn into lithium electricity positive electrode of new generation.
At present, commercialized NCM tertiary cathode materials are used on the battery that charging voltage is 4.2V, its specific capacitance model
Enclose for 140~200mAh/g；And realize that higher utilization ternary material is theoretical in itself by improving charging voltage (＞ 4.3V)
Capacity (275mAh/g), phase in version or crystal grain efflorescence, transition metal dissolution and electrochemical dissolution of ternary material etc. can be aggravated
The degree of bad side reaction causes capacity attenuation to increase severely.Particularly, commercialized NCM positive electrodes are mostly by primary particle at present
Assemble the spherical or spherical second particle formed, this pattern can be such that material easily occurs in the roll-in for prepare electrode slice
Second particle crushes, and aggravates the side reaction between material and electrolyte, causes that stability of the material under high voltage condition is poor, circulates
Short life, so as to significantly limit application of the ternary material in powerful device.
Therefore, cyclical stability of the ternary material under high voltage condition how is improved, electrode side reaction degree is reduced, is
Ternary material meets higher volume energy, the key of more longlasting endurance.And report now about preparing monocrystalline ternary material
Method, be by high temperature (1000 DEG C of ＞), (＞ 12h) sintering obtains the preferable shape of single crystal grain shape for a long time mostly
Looks, the monocrystalline ternary material that this kind of method obtains because cation mixing degree is larger, individual particle footpath is larger make material have compared with
Low first all coulombic efficiencies, reduce the capacity usage ratio of material.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of high voltage type
Class monocrystalline tertiary cathode material, specially a kind of monocrystalline cobalt nickel lithium manganate ternary material LiNixCoyMn1-x-yO2, it has similar
Monocrystalline pattern, average grain diameter (D50) are 3~7 μm, and have higher first all coulombic efficiencies (~90%) and good high voltage
Cyclical stability.
Another object of the present invention is to provide a kind of preparation method of above-mentioned high voltage type class monocrystalline tertiary cathode material.
The inventive method has relatively low sintering temperature (950 DEG C of ＜) and shorter sintering time relative to existing method
(≤12h), you can obtain the nickel-cobalt lithium manganate cathode material that the average grain diameter (D50) with single crystal-like pattern is 3~7 μm.
The purpose of the present invention is realized by following proposal：
A kind of preparation method of high voltage type class monocrystalline tertiary cathode material, comprises the following steps：
(1) by nickel salt, cobalt salt, manganese salt, ammoniacal liquor complexing agent and ammonium oxalate the precipitating reagent hybrid reaction in aqueous systems, nickel is obtained
Cobalt manganese oxalate precursor；
(2) nickel cobalt manganese oxalate precursor is mixed with lithium source, 3~6h of ball milling, is mixed under 100~400r/min
Material；
(3) compound is placed in atmosphere furnace, is passed through air or oxygen atmosphere, then heated up with 1~10 DEG C of programming rate
To 450~750 DEG C, normal temperature is naturally cooling to after 4~10h of Isothermal sinter, obtains pre-burning thing；
(4) by pre-burning thing under 400~750r/min 5~8h of ball mill grinding, obtain crushed material；
(5) crushed material is mixed with lithium source, 1~4h of ball milling mixing under 100~400r/min, obtains being pulverized and mixed material；
(6) material will be pulverized and mixed to be placed in atmosphere furnace, and will be passed through oxygen atmosphere, 450 are warming up to 3~10 DEG C/min speed~
600 DEG C, 2~6h of calcining at constant temperature, after being then warming up to 750~950 DEG C of 8~12h of calcining at constant temperature again with 1~5 DEG C/min speed
Room temperature is cooled to stove, most obtains high voltage type class monocrystalline tertiary cathode material after broken, crushing, sieving afterwards.
Nickel salt described in step (1), cobalt salt, the mol ratio of manganese salt are x：y：1-x-y, wherein 0.3≤x≤0.85,0.1≤
y≤0.4。
The technique of hybrid reaction described in step (1) is preferably to be stirred at 40~55 DEG C, and ageing reaction 15~
20h.The stirring is preferably 200~300rpm.
The amount of ammoniacal liquor complexing agent used is defined by adjusting reaction system pH for 5~6.5 in step (1).
Ammonium oxalate precipitation dosage used is always rubbed with oxalate denominationby and metal ion in nickel salt, cobalt salt, manganese salt in step (1)
The 1 of that number:1.5~1:2 are defined.
The nickel cobalt manganese oxalate precursor obtained described in step (1), it is the ternary grass of 5~12 μm of average grain diameter (D50)
Hydrochlorate NixCoyMn1-x-yC2O4, wherein 0.3≤x≤0.85,0.1≤y≤0.4.
The mol ratio of nickel cobalt manganese oxalate precursor and lithium source is according to Li/Me=0.6 described in step (2):1~0.8:1,
Li is the elemental lithium mole in lithium source, and Me is the nickel in presoma, cobalt, the mole sum of manganese element.
Pre-burning thing described in step (3) is to react the oxide Li of generation after presoma and lithium source dehydrationz-
NixCoyMn1-x-y-O2, wherein z is 0.6~0.8.
Crushed material described in step (4) is the oxide Li that average grain diameter (D50) is 2~5 μmz-NixCoyMn1-x-y-
O2, wherein z is 0.6~0.8.
The mol ratio of crushed material and lithium source is according to Li/Me=0.31 described in step (5):1~0.49:1, Li is in lithium source
Elemental lithium mole, Me is nickel in crushed material, cobalt, the mole sum of manganese element.
Preferably, described nickel salt is at least one of nickel sulfate and nickel acetate.
Preferably, described cobalt salt is at least one of cobaltous sulfate and cobalt acetate.
Preferably, described manganese salt is at least one of manganese sulfate and manganese acetate.
Preferably, described lithium source is at least one of lithium hydroxide and lithium carbonate.
The high voltage type class monocrystalline tertiary cathode material that the inventive method is prepared, its chemical formula are
LiNixCoyMn1-x-yO2, wherein, 0.3≤x≤0.85,0.1≤y≤0.4.
There is the high voltage type class monocrystalline NCM tertiary cathode materials of the present invention single crystal-like pattern, average grain diameter (D50) to be
3~7 μm, and there is higher first all coulombic efficiencies (~90%) and good high voltage cycle stability.
The present invention is had the following advantages and beneficial effect relative to prior art：
High voltage type class monocrystalline tertiary cathode material provided by the present invention, nickel cobalt manganese grass is obtained by precipitating reagent of ammonium oxalate
Hydrochlorate presoma, and by the technique of secondary mixed lithium, separating twice and double sintering, be able to can be obtained under lower sintering temperature
Monocrystalline pattern is preferable, size distribution is more uniform, and has higher compacted density, higher first all coulombic efficiencies and good height
Press the class monocrystalline NCM tertiary cathode materials of cyclical stability.
Brief description of the drawings
Fig. 1 is SEM (SEM) figure of the class monocrystalline tertiary cathode material of embodiment 1；
Fig. 2 be embodiment 1 class monocrystalline tertiary cathode material under the conditions of 4.35V, 0.5C 25 DEG C and 45 DEG C of cyclicity
Can figure；
Fig. 3 is SEM (SEM) figure of the class monocrystalline tertiary cathode material of embodiment 2；
Fig. 4 is the normal temperature (25 DEG C) and high temperature that the class monocrystalline tertiary cathode material of embodiment 2 is tested under 4.35V, 0.2C
The first charge-discharge curve of (45 DEG C)；
Fig. 5 is SEM (SEM) figure for the class monocrystalline tertiary cathode material for applying example 3.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of the present invention.
The material being related in the following example can obtain from commercial channel.
Embodiment 1
1) stoichiometrically 1:1:1, which weighs nickel sulfate, cobaltous sulfate, manganese sulfate, is dissolved in deionized water, is made into metal
Cation total concentration is 2mol/L mixed liquor, and stirs and be sufficiently mixed it uniformly to obtain mixing salt solution.
2) 5mol/L ammonium oxalate precipitant solution and 8mol/L ammonia spirit are prepared respectively；Then by above-mentioned mixing
Salting liquid is pumped into reactor with 10L/h speed, while by controlling the flow velocity of ammonium oxalate solution and ammonia spirit to make salt-mixture
The pH value of solution is 6.5, and ammonium oxalate precipitation dosage used is always rubbed with oxalate denominationby and metal ion in nickel salt, cobalt salt, manganese salt
The 1 of that number:1.5~1:2 are defined, and it is 50 DEG C that course of reaction, which controls temperature of reaction kettle, mixing speed 200r/min；Treat metal sun
Ar ion mixing liquid is all pumped into ageing reaction 20h after reactor；Then by the reacted isolated reaction of product centrifugal filtration
Sediment, and the SO cleaned with deionized water into sediment4 2+Percentage amounts (wt%) are less than 0.2%, finally by the production after washing
Thing is dried at 105~120 DEG C, and it is Ni to obtain molecular formula1/3Co1/3Mn1/3C2O4Oxalate precipitation thing presoma.
3) 5.000Kg Ni is weighed respectively1/3Co1/3Mn1/3C2O4With 0.890Kg Li2CO3Add in ball grinder,
Ball milling 3h under 200r/min, obtain well mixed compound；Then compound is placed in atmosphere furnace, is passed through 5L/min sky
Gas, it is heated to 800 DEG C with 5 DEG C/min programming rates, is cooled to room temperature with stove after calcining at constant temperature 8h, obtains pre-burning thing Li0.7-
Ni1/3Co1/3Mn1/3O2。
4) pre-burning thing is placed in ball grinder, the ball mill grinding 8h under 600r/min, obtains described crushed material；Then will
0.458Kg Li2CO3It is put into and crushes in ball grinder, ball milling 2h obtains being pulverized and mixed material under 200r/min.
5) material will be pulverized and mixed to be placed in atmosphere furnace, and will be passed through oxygen atmosphere, 750 DEG C of perseverances are warming up to 3 DEG C/min speed
Temperature calcining 6h, then 930 DEG C of calcining at constant temperature 10h are warming up to 3 DEG C/min DEG C of speed, room temperature then is cooled to stove, is most passed through afterwards
Broken, crushing, 300 mesh sieves excessively obtain class monocrystalline LiNi1/3Co1/3Mn1/3O2(LNCM-111)。
Test analysis is carried out to the LNCM-111 obtained in embodiment 1 using Scanning Electron microscope (SEM), obtains it
SEM schemes, as shown in Figure 1.As seen from Figure 1, LNCM-111 manufactured in the present embodiment be average grain diameter be 4.5 μm, monocrystalline pattern compared with
Complete particle.The LNCM-111 prepared by this implementation profit is fabricated to positive plate, compaction area using roll squeezer and slicer
For 1.54cm2, pressure 80T, compacted density 4.2g/cm3。
The LNCM-111 obtained in example 1 is assembled into 2430 type button cells, carried out under conditions of 4.35V, 0.2C
Charge-discharge test, first discharge specific capacity, first all coulombic efficiencies are respectively 152.6mAhg under normal temperature (25 DEG C)-1With 90.0%,
Specific capacitance is put under high temperature (45 DEG C) first, first all coulombic efficiencies are respectively 156.5mAhg-1With 90.5%；Then in high electricity
Press and normal temperature (25 DEG C) and high temperature (45 DEG C) cycle performance is tested under (4.35V), 0.5C：At 25 DEG C the specific discharge capacity of the 50th week and
Capacity retention rate is respectively 148.2mAhg-1, 97.1%, the 50th week at 45 DEG C puts specific capacitance and capacity retention rate difference
For 148.7mAhg-1, 95.0%, as shown in Figure 2.
Embodiment 2
1) stoichiometrically 6:2:2, which weigh nickel acetate, cobalt acetate, manganese acetate, is dissolved in deionized water, is made into metal
Cation total concentration is 1.5mol/L mixed liquor, and stirs and be sufficiently mixed it uniformly to obtain mixing salt solution.
2) 3mol/L ammonium oxalate precipitant solution and 6mol/L ammonia spirit are prepared respectively；Then by above-mentioned mixing
Salting liquid is pumped into reactor with 10L/h speed, while by controlling the flow velocity of ammonium oxalate solution and ammonia spirit to make salt-mixture
The pH value of solution is 6, and ammonium oxalate precipitation dosage used is with metal ion total moles in oxalate denominationby and nickel salt, cobalt salt, manganese salt
Several 1:1.5~1:2 are defined, and it is 50 DEG C that course of reaction, which controls temperature of reaction kettle, mixing speed 300r/min；Treat metal sun from
Sub- mixed liquor is all pumped into ageing reaction 16h after reactor；Then it is the isolated reaction of reacted product centrifugal filtration is heavy
Starch, and the SO cleaned with deionized water into sediment4 2+Percentage amounts (wt%) are less than 0.2%, finally by the product after washing
Dried at 105~120 DEG C, it is Ni to obtain molecular formula0.6Co0.2Mn0.2C2O4Oxalate precipitation thing presoma.
3) 6.000Kg Ni is weighed respectively0.6Co0.2Mn0.2C2O4With 1.214Kg Li2CO3Add in ball grinder,
Ball milling 3h under 300r/min, obtain well mixed compound；Then compound is placed in atmosphere furnace, is passed through 5L/min sky
Gas, it is heated to 750 DEG C with 5 DEG C/min programming rates, is cooled to room temperature with stove after calcining at constant temperature 8h, obtains pre-burning thing Li0.8-
Ni0.6Co0.2Mn0.2O2。
4) pre-burning thing is placed in ball grinder, the ball mill grinding 8h under 800r/min, obtains described crushed material；Then will
0.482Kg LiOHH2O, which is put into, to be crushed in ball grinder, and ball milling 3h obtains being pulverized and mixed material under 200r/min.
5) material will be pulverized and mixed to be placed in atmosphere furnace, and will be passed through oxygen atmosphere, 500 DEG C of perseverances are warming up to 4 DEG C/min speed
Temperature calcining 5h, then 870 DEG C of calcining at constant temperature 12h are warming up to 3 DEG C/min DEG C of speed, room temperature then is cooled to stove, is most passed through afterwards
Broken, crushing, 300 mesh sieves excessively obtain class monocrystalline LiNi0.6Co0.2Mn0.2O2(LNCM-622)。
Test analysis is carried out to the LNCM-622 obtained in embodiment 2 using Scanning Electron microscope (SEM), obtains it
SEM schemes, as shown in Figure 3.As seen from Figure 3, LNCM-622 manufactured in the present embodiment be average grain diameter be 3.86 μm, monocrystalline pattern compared with
Complete particle.The LNCM-622 of preparation is fabricated to positive plate, compaction area 1.54cm2, pressure 80T, compacted density is
4.0g/cm3。
The LNCM-622 obtained in example 2 is assembled into 2430 type button cells, tests 4.35V normal temperature and high temperature (45 DEG C)
Under first charge-discharge performance, first discharge specific capacity, first all coulombic efficiencies are respectively 180.2mAhg under normal temperature (25 DEG C)-1With
90.2%, first discharge specific capacity, first all coulombic efficiencies are respectively 184.8mAhg under high temperature (45 DEG C)-1With 90.9%, as a result
As shown in Figure 4；Then normal temperature (25 DEG C) and high temperature (45 DEG C) cycle performance is tested under high voltage (4.35V), 0.5C：At 25 DEG C
The specific discharge capacity and capacity retention rate of the 50th week is respectively 148.2mAhg-1, 97.1%, the electric discharge ratio of the 50th week at 45 DEG C
Capacity and capacity retention rate are respectively 148.7mAhg-1, 95.0%, as shown in Figure 2.
Embodiment 3
1) stoichiometrically 0.85:0.1:0.05, which weighs nickel sulfate, cobaltous sulfate, manganese sulfate, is dissolved in deionized water,
The mixed liquor that metal cation total concentration is 1.8mol/L is made into, and stirs and is sufficiently mixed it uniformly to obtain mixing salt solution.
2) 4mol/L ammonium oxalate precipitant solution and 8mol/L ammonia spirit are prepared respectively；Then by above-mentioned mixing
Salting liquid is pumped into reactor with 12L/h speed, while by controlling the flow velocity of ammonium oxalate solution and ammonia spirit to make salt-mixture
The pH value of solution is 5.5, and ammonium oxalate precipitation dosage used is always rubbed with oxalate denominationby and metal ion in nickel salt, cobalt salt, manganese salt
The 1 of that number:1.5~1:2 are defined, and it is 50 DEG C that course of reaction, which controls temperature of reaction kettle, mixing speed 250r/min；Treat metal sun
Ar ion mixing liquid is all pumped into ageing reaction 18h after reactor；Then by the reacted isolated reaction of product centrifugal filtration
Sediment, and the SO cleaned with deionized water into sediment4 2+Percentage amounts (wt%) are less than 0.2%, finally by the production after washing
Thing is dried at 105~120 DEG C, and it is Ni to obtain molecular formula0.85Co0.1Mn0.05C2O4Oxalate precipitation thing presoma.
3) 5.000Kg Ni is weighed respectively0.85Co0.1Mn0.05C2O4With 0.902Kg LiOHH2O is added in ball grinder,
The ball milling 3h under 300r/min, obtains well mixed compound；Then compound is placed in atmosphere furnace, is passed through 5L/min's
Oxygen, it is heated to 500 DEG C with 5 DEG C/min programming rates, is cooled to room temperature with stove after calcining at constant temperature 8h, obtains pre-burning thing Li0.63-
Ni0.85Co0.1Mn0.05O2。
4) pre-burning thing is placed in ball grinder, the ball mill grinding 5h under 600r/min, obtains described crushed material；Then will
0.482Kg LiOHH2O, which is put into, to be crushed in ball grinder, and ball milling 3h obtains being pulverized and mixed material under 200r/min.
5) material will be pulverized and mixed to be placed in atmosphere furnace, and will be passed through oxygen atmosphere, 500 DEG C of perseverances are warming up to 4 DEG C/min speed
Temperature calcining 4h, then 790 DEG C of calcining at constant temperature 11h are warming up to 3 DEG C/min DEG C of speed, room temperature then is cooled to stove, is most passed through afterwards
Broken, crushing, 300 mesh sieves excessively obtain class monocrystalline LiNi0.85Co0.1Mn0.05O2(LNCM-7.5)。
Test analysis is carried out to the LNCM-8.5 obtained in embodiment 3 using Scanning Electron microscope (SEM), obtains it
SEM schemes, as shown in Figure 5.As seen from Figure 5, LNCM-8.5 manufactured in the present embodiment be average grain diameter be 5.34 μm, monocrystalline pattern compared with
Complete particle.The LNCM-8.5 of preparation is fabricated to positive plate, compaction area 1.54cm2, pressure 80T, compacted density is
4.3g/cm3。
The LNCM-8.5 obtained in example 3 is assembled into 2430 type button cells, tests 4.35V normal temperature and high temperature (45 DEG C)
Under first charge-discharge performance, first discharge specific capacity, first all coulombic efficiencies are respectively 212.3mAhg under normal temperature (25 DEG C)-1With
89.8%, the first all coulombic efficiencies of first discharge specific capacity are respectively 215.8mAhg under high temperature (45 DEG C)-1With 90.3%；Then
Normal temperature (25 DEG C) and high temperature (45 DEG C) cycle performance is tested under high voltage (4.35V), 0.5C：The electric discharge ratio of the 50th week at 25 DEG C
Capacity and capacity retention rate are respectively 197.2mAhg-1, 92.9%, the specific discharge capacity of the 50th week and capacity retain at 45 DEG C
Rate is respectively 194.6mAhg-1, 90.2%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high voltage type class monocrystalline tertiary cathode material, it is characterised in that comprise the following steps：
(1) by nickel salt, cobalt salt, manganese salt, ammoniacal liquor complexing agent and ammonium oxalate the precipitating reagent hybrid reaction in aqueous systems, nickel cobalt manganese is obtained
Oxalate precursor；
(2) nickel cobalt manganese oxalate precursor is mixed with lithium source, 3~6h of ball milling, obtains compound under 100~400r/min；
(3) compound is placed in atmosphere furnace, is passed through air or oxygen atmosphere, be then warming up to 450 with 1~10 DEG C of programming rate
~750 DEG C, normal temperature is naturally cooling to after 4~10h of Isothermal sinter, obtains pre-burning thing；
(4) by pre-burning thing under 400~750r/min 5~8h of ball mill grinding, obtain crushed material；
(5) crushed material is mixed with lithium source, 1~4h of ball milling mixing under 100~400r/min, obtains being pulverized and mixed material；
(6) material will be pulverized and mixed to be placed in atmosphere furnace, and will be passed through oxygen atmosphere, 450~600 are warming up to 3~10 DEG C/min speed
DEG C, 2~6h of calcining at constant temperature, then it is warming up to again with 1~5 DEG C/min speed after 750~950 DEG C of 8~12h of calcining at constant temperature with stove
Room temperature is cooled to, most obtains high voltage type class monocrystalline tertiary cathode material after broken, crushing, sieving afterwards.
2. the preparation method of high voltage type class monocrystalline tertiary cathode material according to claim 1, it is characterised in that：Step
(1) nickel salt described in, cobalt salt, the mol ratio of manganese salt are x：y：1-x-y, wherein 0.3≤x≤0.85,0.1≤y≤0.4.
3. the preparation method of high voltage type class monocrystalline tertiary cathode material according to claim 1, it is characterised in that：Step
(2) mol ratio of nickel cobalt manganese oxalate precursor described in and lithium source is according to Li/Me=0.6:1~0.8:1, Li is in lithium source
Elemental lithium mole, Me are the nickel in presoma, cobalt, the mole sum of manganese element.
4. the preparation method of high voltage type class monocrystalline tertiary cathode material according to claim 1, it is characterised in that：Step
(5) mol ratio of crushed material described in and lithium source is according to Li/Me=0.31:1~0.49:1, Li is the elemental lithium mole in lithium source
Amount, Me are nickel in crushed material, cobalt, the mole sum of manganese element.
5. the preparation method of high voltage type class monocrystalline tertiary cathode material according to claim 1, it is characterised in that：It is described
Nickel salt be at least one of nickel sulfate and nickel acetate；Described cobalt salt is at least one of cobaltous sulfate and cobalt acetate；Institute
The manganese salt stated is at least one of manganese sulfate and manganese acetate；Described lithium source is at least one in lithium hydroxide and lithium carbonate
Kind.
6. the preparation method of high voltage type class monocrystalline tertiary cathode material according to claim 1, it is characterised in that：Step
(1) technique of hybrid reaction described in is is stirred at 40~55 DEG C, 15~20h of ageing reaction.
7. the preparation method of high voltage type class monocrystalline tertiary cathode material according to claim 1, it is characterised in that：Step
(1) amount of ammoniacal liquor complexing agent used is defined by adjusting reaction system pH for 5~6.5 in.
8. the preparation method of high voltage type class monocrystalline tertiary cathode material according to claim 1, it is characterised in that：Step
(1) ammonium oxalate precipitation dosage used is with 1 of metal ion total mole number in oxalate denominationby and nickel salt, cobalt salt, manganese salt in:1.5
~1:2 are defined.
9. a kind of high voltage type class monocrystalline tertiary cathode material, it is characterised in that according to the system described in any one of claim 1~8
Preparation Method obtains.
10. high voltage type class monocrystalline tertiary cathode material according to claim 9, it is characterised in that its chemical formula is
LiNixCoyMn1-x-yO2, wherein, 0.3≤x≤0.85,0.1≤y≤0.4.
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