CN109273701A - High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material and preparation method thereof - Google Patents
High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material and preparation method thereof Download PDFInfo
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- 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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Abstract
High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material and preparation method thereof, the tertiary cathode material are its chemical formula are as follows: LiNixCoyMn(1‑x‑y)O2, wherein 0.70≤x≤0.85,0.05≤y≤0.20,1-x-y > 0, by the nickelic core-shell structure particles that just core, middle layer and shell form；Nickel element is uniformly distributed in nickelic just core, and is gradually successively decreased since middle layer to shell, and cobalt element is uniformly distributed in nickelic just core, middle layer and shell, and manganese element is gradually increased since middle layer to shell.The invention also discloses the preparation methods of the tertiary cathode material.Tertiary cathode material made by the present invention is assembled into battery, specific discharge capacity height, circulation and good rate capability；The method of the present invention simple process, it is at low cost, be suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of nickel-cobalt-manganternary ternary anode materials and preparation method thereof, and in particular to a kind of high nickel core-shell structure
Gradient nickel-cobalt-manganternary ternary anode material and preparation method thereof.
Background technique
Extensive energy shortages is got worse with the problem of environmental pollution in the 21st century, world wide, forces people
Seek that traditional fossil energy can be substituted, and the green power supply system of new energy (solar energy, wind energy and nuclear energy etc.) can be stored.
Lithium ion battery, with excellent energy density, high rate performance and long life, is widely applied to mobile phone, number by it
In the code equipment such as camera and pocket pc, and its application target is just automobile-used from small type mobile devices to Large Electric vehicle
Battery string, such as the Vehicular battery of pure electric vehicle, hybrid electric vehicle and plug-in hybrid electric vehicles, with energy storage system etc.
Aspect transformation.For lithium ion battery applications into large-sized power battery and energy storage cells, key is that energy density, power are close
The five aspect factor such as degree, service life, safety and price.Wherein, when solving these problems, battery assembly technology and electricity should be optimized
Pond management system, again from the building block of lithium-ion battery system, such as positive electrode, negative electrode material, diaphragm and electrolyte
Aspect is strengthened.In lithium-ion battery system, positive electrode restricts the development of battery overall performance.Ternary material conduct
One of anode material for lithium-ion batteries is generally acknowledged most to have due to the advantages that its voltage is high, specific capacity is high, low in cost
One of anode material for lithium-ion batteries of development prospect.
CN103700845A discloses a kind of preparation method of nickel-cobalt-manganese ternary material, is by configuring three kinds of various concentrations
Manganese sulfate, nickel sulfate, cobalt sulfate solution and three kinds of various concentrations sodium hydroxide and ammonia spirit, using different plus
Material sequence preparation gradient anode ternary material.But performance of the material under high magnification is bad, under the voltage of 5C multiplying power, puts
Electric specific capacity only has 150mAh/g.
CN106058238A discloses a kind of preparation method of nickel-cobalt-manganese ternary material, be using nickel, cobalt, manganese it is solvable
Salt, using oxide as precipitating reagent, by coprecipitation for nickel-cobalt-manganese ternary material precursor, then in ternary material precursor plus
Enter lithium fluoride, lithium carbonate, magnesium acetate, carries out ball milling sintering.Although tertiary cathode material is prepared using coprecipitation in this method
Material, and adulterated using fluorine, magnesium, its circulation and high rate performance are improved, still, synthesis technology is cumbersome, is unfavorable for market-oriented big rule
Mould production.
Generally for height ratio capacity is obtained, the accounting of nickel element in ternary material will increase, still, nickelic ternary material
Multiplying power and cycle performance are poor, therefore, how while ternary material has high capacity density, can have relatively good
Circulation and high rate performance become one of the research emphasis of scientific research personnel.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of electric discharge ratio
The high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material of capacity height, circulation and good rate capability.
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of technique letter
The preparation method of high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material that is single, at low cost, being suitable for industrialized production.
The technical solution adopted by the present invention to solve the technical problems is as follows: high nickel core-shell structure gradient nickel-cobalt-manganese ternary is just
Pole material, chemical formula are as follows: LiNixCoyMn(1-x-y)O2, wherein 0.70≤x≤0.85,0.05≤y≤0.20,1-x-y > 0,
By the nickelic core-shell structure particles that just core, middle layer and shell form；Nickel element is just uniformly distributed in core nickelic, and from middle layer
Start gradually to successively decrease to shell, cobalt element is uniformly distributed in nickelic just core, middle layer and shell, and manganese element is since middle layer to shell
Layer gradually increases.The nickelic just core of tertiary cathode material of the present invention is fine and close, enables to the functionally gradient material (FGM) compared to traditional full ladder
Degree material provides high capacity in the case where guaranteeing Thickness of Gradient Layer；And middle layer is more loose gradient layer, first in lithium ion
When insertion, certain structure buffering can be played, structural failure is inhibited, secondly, can inhibit cationic mixing, promotes material property；
And carbonate shell then further provides structural defence effect for material granule, prevents particle because of big multiplying power or multi-cycle charge and discharge
And it is damaged.
Preferably, the average grain diameter of the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material is 4~8 μm.
Preferably, the average diameter of the nickelic just core is 0.5~1.5 μm.If nickelic just core average diameter is excessive, can
So that its cationic mixing degree in charge and discharge process increases, reduce the inhibition cation mixing effect of gradient layer.
Preferably, the average thickness in the middle layer is 3.0~6.5 μm.If the thickness in middle layer is too small, cation can be inhibited
The effect of mixing is lower, if the thickness in middle layer is excessive, will increase grain diameter, is unfavorable for mentioning for material circulation high rate performance
It is high.
Preferably, the average thickness of the shell is 1~2 μm.If the thickness of shell is too small, the protection to material structure
It acts on unobvious, if the thickness of shell is excessive, will affect the infiltration of electrolyte.
Preferably, the nickelic just core is LiNi0.9Co0.1O2。
Preferably, the middle layer is the mixed resulting nickle cobalt lithium manganate of lithium after the co-precipitation of nickel cobalt manganese hydroxide precipitating reagent.
Preferably, the shell is the mixed resulting nickle cobalt lithium manganate of lithium after nickel cobalt manganese carbonate deposition agent co-precipitation.
Preferably, it is 12~20% that the nickel in the nickelic just core, which accounts for the molar percentage of total nickel content,.
Preferably, the nickel content accounts for the sum of each layer nickel, cobalt and manganese total mole number in nickelic just core, middle layer or shell
Percentage be 95~70%.
Preferably, in middle level or in shell, the percentage for accounting for the sum of each layer nickel, cobalt and manganese total mole number is the manganese content
> 0~20%.
In nickelic just core, middle layer or the shell of tertiary cathode material of the present invention, the sum of nickel, cobalt, manganese mole percent are
100%。
It is as follows that the present invention further solves technical solution used by its technical problem: high nickel core-shell structure gradient nickel cobalt manganese
The preparation method of tertiary cathode material, comprising the following steps:
(1) high nickel content nickel and cobalt solution is pumped into the reaction kettle equipped with ammonia spirit, and stirred, formation average grain diameter 0.5~
1.5 μm nickelic is pumped into high nickel content nickel and cobalt solution just after core, then by low nickel content nickel cobalt manganese solution, is mixed, with this
Meanwhile the high nickel content nickel and cobalt solution for being constantly pumped into low nickel content nickel cobalt manganese solution is pumped into formed it is nickelic just core ammonium hydroxide it is molten
In the reaction kettle of liquid, at the same with ammonium hydroxide adjust reaction system ammonia concn, with hydroxide precipitant solution adjust reactant
It is pH value, stirring carries out coprecipitation reaction and obtains presoma nuclear material until grain diameter grows to 3~7 μm, continues above-mentioned
Operation, only replaces with the pH value that carbonate deposition agent solution is used to adjust reaction system for hydroxide precipitant solution, stirs
Coprecipitation reaction is carried out, until low nickel content nickel cobalt manganese solution and the charging of high nickel content nickel and cobalt solution finish, is obtained containing presoma core
The solution of Shell Materials；
(2) the solution stirring obtained by step (1) containing presoma nucleocapsid layer material is aged, filters, washs, it is dry, it obtains
High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material presoma；
(3) in the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material presoma obtained by step (2), lithium source is added, grinds,
After pre-burning, sintering obtains high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material.
The feed way of the method for the present invention creativeness forms comparatively dense nickelic just core, gradually forms later opposite
The full gradient layer of loose nickel cobalt manganese is excessive, finally re-forms the ternary material precursor of carbonate shell.
Preferably, in step (1), the high nickel content nickel cobalt manganese solution and constantly it is pumped into low nickel content nickel cobalt manganese solution
The charging rate of high nickel content nickel and cobalt solution be 40~120mL/h, the charging rate of the low nickel content nickel cobalt manganese solution is
20~60mL/h.The too fast or too slow speed of growth that will lead to each layer of material of the charging rate is uneven.
Preferably, in step (1), in the high nickel content nickel and cobalt solution, the concentration of metal ion is 1~3mol/L, Ni
It is 5~30% that the molar percentage for accounting for total metal ion, which is the molar percentage that 70~95%, Co accounts for total metal ion, Ni, Co from
Sub- summation is 100%.
Preferably, in step (1), in the low nickel content nickel cobalt manganese solution, the concentration of metal ion is 1~3mol/L,
It is the molar percentage that 60~80%, Co accounts for total metal ion is that 10~30%, Mn is accounted for that Ni, which accounts for the molar percentage of total metal ion,
The molar ratio of total metal ion is 10~30%, and Ni, Co, Mn ion summation are 100%.Under the ratio and concentration, facilitate
Form low nickel middle layer and Shell Materials.
Preferably, in step (1), in same reaction system, the nickel content of low nickel content nickel cobalt manganese solution is lower than nickelic
The nickel content of content nickel and cobalt solution.
Preferably, in step (1), ammonia spirit, low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt are molten in reaction kettle
The volume ratio of liquid is 0.1~1.0:0.8~1.2:1.The ratio is conducive to the beginning of coprecipitation reaction and the control of material gradient
System.
Preferably, in step (1), the molar concentration of the ammonia spirit is 0.3~0.5mol/L.
Preferably, in step (1), reaction system ammonia concn is adjusted with ammonium hydroxide and is maintained at 0.3~0.5mol/L.The present invention
The method titrated using acid solution detects molar concentration of the ammonium hydroxide in entire reaction process reaction system, to control ammonium hydroxide
Additional amount keeps ammonia concn.The ammonia concn is conducive to control the surface topography of particle.
Preferably, in step (1), the mass concentration of the ammonium hydroxide for adjusting reaction system ammonia concn is 25~28%.
Preferably, in step (1), with hydroxide precipitant solution adjust pH value of reaction system be maintained at 10.5~
11.5.At the pH, it is ensured that the particle middle layer speed of growth will not be too fast or too slow.
Preferably, in step (1), the molar concentration of the hydroxide precipitant solution is 5~10mol/L.
Preferably, in step (1), the hydroxide precipitating reagent is in sodium hydroxide, potassium hydroxide or lithium hydroxide etc.
One or more.
Preferably, in step (1), pH value of reaction system is adjusted with carbonate deposition agent solution and is maintained at 8.5~10.5.?
Under the pH, it is ensured that the particle shell speed of growth will not be too fast or too slow.
Preferably, in step (1), the molar concentration of the carbonate deposition agent solution is 0.5~1.5mol/L.
Preferably, in step (1), the carbonate deposition agent is sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate or carbon
One or more of potassium hydrogen phthalate etc..
Preferably, in step (1), the co-precipitation for generating presoma nuclear material and generating presoma nucleocapsid layer material is anti-
Ying Zhong, the speed of stirring are 600~1200r/min, and temperature is 50~70 DEG C.The mixing speed is more advantageous to granulated
The formation of looks, the temperature are more advantageous to the progress of reaction.
The present invention generates the grain diameter during presoma nuclear material using laser particle size analyzer measurement, anti-to judge
Answer terminal.
Preferably, in step (1), the high nickel content nickel and cobalt solution and low nickel content nickel cobalt manganese solution are soluble nickel
The mixed solution of one or more of salt, soluble cobalt or soluble manganese salt.
Preferably, in step (1), the soluble nickel salt is one of nickel sulfate, nickel nitrate, nickel acetate or nickel chloride
Or it is several.
Preferably, in step (1), the soluble cobalt is one of cobaltous sulfate, cobalt nitrate, cobalt acetate or cobalt chloride
Or it is several.
Preferably, in step (1), the solubility manganese salt is one of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride
Or it is several.
Preferably, in step (2), the speed of the stirring is 400~800r/min.
Preferably, in step (2), the temperature of the ageing is 50~80 DEG C, and the time is 5~15h.The aging condition has
Grow more evenly conducive to particle.If drying temperature is too low, drying time is too long, if drying temperature is excessively high, there will be secondary anti-
It should occur.
Preferably, in step (2), the temperature of the drying is 50~100 DEG C, and the time is 5~15h.
Preferably, elemental lithium and high nickel core-shell structure gradient nickel-cobalt-manganese ternary anode material in step (3), in the lithium source
The molar ratio of the sum of molal quantity of nickel, cobalt, manganese element is 1.01~1.08:1 in material precursor.If mixed lithium molar ratio is too low,
Elemental lithium can be insufficient, can reduce specific discharge capacity；If mixed lithium molar ratio is excessively high, active material ratio reduces, and can also reduce and put
Electric specific capacity.
Preferably, in step (3), the lithium source be lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate or lithium acetate and
One or more of their hydrate etc..
Preferably, in step (3), the time of the grinding is 5~10min.If milling time is too short, mixing can be made not
Uniformly, if milling time is too long, material structure can be destroyed.
Preferably, in step (3), the temperature of the pre-burning is 350~550 DEG C, and the time is 3~6h.Pre-burning be in order to
Make material mixing in microcosmic point more evenly, if calcined temperature is too low or burn-in time is too short, it is uneven to will lead to mixing,
If calcined temperature is excessively high or burn-in time is too long, energy waste will lead to.
Preferably, in step (3), the temperature of the sintering is 650~950 DEG C, the time is 8~for 24 hours.If the temperature of sintering
Too low or sintering time is too short, then will lead to material reaction not exclusively, and crystal form is imperfect, so that material property is influenced, if burning
The temperature of knot is excessively high or overlong time, then will lead to the generation of side reaction, to influence material property.
Preferably, in step (3), the heating rate of the pre-burning and sintering is 3~5 DEG C/min.
Beneficial effects of the present invention are as follows:
(1) the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material of the present invention is made of nickelic just core, middle layer and shell
The core-shell structure particles that average grain diameter is 4~8 μm；The average diameter of the nickelic just core is 0.5~1.5 μm；The middle layer
Average thickness is 3.0~6.5 μm；The average thickness of the shell is 1~2 μm；Nickel element is uniformly distributed in nickelic just core, and
Gradually successively decrease since middle layer to shell, cobalt element is uniformly distributed in nickelic just core, middle layer and shell, and manganese element is opened from middle layer
Begin to shell to gradually increase；Nickelic just core densification offer high capacity in the tertiary cathode material, and the gradient that middle layer is loose
Layer makes lithium ion more unobstructed in deintercalation process, may also suppress structural failure, promotes material property, carbonate shell is then into one
Step provides structural defence effect, guarantees the circulation and high rate performance of ternary material；
(2) the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material of the present invention is assembled into battery, in 2.5~4.5V, 0.1C
Under the current density of (20mA/g), for the first time under current density of the discharge capacity for 199mAh/g, 10C(2000mA/g), discharge ratio
Capacity is 140mAh/g, illustrates specific discharge capacity height, good rate capability；100 circle of circulation, specific capacity still may be used under 1C(200mA/g)
Up to 162mAh/g, capacity retention ratio may be up to 87.3%, illustrate good cycle；
(3) the method for the present invention simple process, it is at low cost, be suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the XRD diagram of the 1 high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material of gained of the embodiment of the present invention；
Fig. 2 is the SEM figure of the 1 high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material of gained of the embodiment of the present invention；
Fig. 3 is the focused ion beam test of the 1 high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material of gained of the embodiment of the present invention
Figure；
Fig. 4 is that the line of tri- kinds of elements of Ni, Co, Mn of Fig. 3 grain section sweeps EDS figure；
Fig. 5 is the first circle of 1 gained high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material institute of embodiment of the present invention assembled battery
Charge and discharge electrograph；
Fig. 6 is the electric discharge of 1 gained high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material institute of embodiment of the present invention assembled battery
Circulation figure；
Fig. 7 is the electric discharge of 1 gained high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material institute of embodiment of the present invention assembled battery
Multiplying power figure；
Fig. 8 is the first circle of 2 gained high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material institutes of embodiment of the present invention assembled battery
Charge and discharge electrograph；
Fig. 9 is the first circle of 3 gained high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material institutes of embodiment of the present invention assembled battery
Charge and discharge electrograph.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Chemical reagent used in the embodiment of the present invention is obtained by routine business approach unless otherwise specified.
High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material embodiment 1
The chemical formula of the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material are as follows: LiNi0.78Co0.11Mn0.11O2, be by
The core-shell structure particles that the average grain diameter of nickelic just core, middle layer and shell composition is 8 μm；It is described it is nickelic just core be
LiNi0.9Co0.1O2, average diameter is 1.2 μm；The middle layer is that mixed lithium is resulting after the agent of nickel cobalt manganese sodium hydroxide pellets is co-precipitated
Nickle cobalt lithium manganate, average thickness are 5.8 μm；The shell is the mixed resulting nickel cobalt of lithium after the co-precipitation of nickel cobalt manganese sodium carbonate precipitating reagent
LiMn2O4, average thickness are 1.0 μm；Nickel element is uniformly distributed in nickelic just core, and is gradually successively decreased since middle layer to shell,
Cobalt element is uniformly distributed in nickelic just core, middle layer and shell, and manganese element is gradually increased since middle layer to shell；It is described nickelic
The molar percentage that nickel in first core accounts for total nickel content is 13~14%；The nickel content nickelic just in core, middle layer or shell,
The percentage for accounting for the sum of each layer nickel, cobalt and manganese total mole number is respectively 90%, < 90~75%, < 75~70%；The manganese content exists
In middle layer or shell, the percentage for accounting for the sum of each layer nickel, cobalt and manganese total mole number is respectively > 0~16%, > 16~20%；It is nickelic
In first core, middle layer or shell, the sum of nickel, cobalt, manganese mole percent are 100%.
As shown in Figure 1, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention is pure phase nickel
Cobalt-manganese ternary positive electrode.
As shown in Fig. 2, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention is average grain
The spheric granules that 8 μm of diameter, pattern are uniform.
As shown in Figure 3,4, in high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention, nickel member
Element is uniformly distributed in nickelic just core, and is gradually successively decreased since middle layer to shell, and cobalt element is in nickelic just core, middle layer and shell
In be uniformly distributed, manganese element is gradually increased since middle layer to shell；The average diameter of nickelic just core is 1.2 μm, and middle layer is put down
With a thickness of 5.8 μm, the average thickness of shell is 1.0 μm.
The preparation method embodiment 1 of high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material
(1) by the 2L high nickel content nickel and cobalt solution (mixed solution of nickel sulfate and cobaltous sulfate, wherein Ni, Co account for total metal ion
Molar percentage is followed successively by 90%, 10%, concentration of metal ions 2mol/L) with charging rate 40mL/h, be pumped into equipped with 2L,
The volume of 0.45mol/L ammonia spirit is and to stir in the reaction kettle of 5L, after forming 1.2 μm of average grain diameter of nickelic just core, then
By the 2L low nickel content nickel cobalt manganese solution (mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, wherein Ni, Co, Mn account for total metal
The molar percentage of ion is followed successively by 70%, 10%, 20%, concentration of metal ions 2mol/L) with charging rate 20mL/h, it is pumped into
In high nickel content nickel and cobalt solution, it is mixed, at the same time, will be constantly pumped into the high nickel content nickel of low nickel content nickel cobalt manganese solution
Cobalt liquor is pumped into and has been formed in the nickelic just reaction kettle of the ammonia spirit of core with charging rate 40mL/h, while using mass concentration
The ammonia concn that 25% ammonium hydroxide adjusts reaction system is maintained at 0.45mol/L, is adjusted with the sodium hydroxide solution of 10mol/L anti-
The pH value of system is answered to be maintained at 11.5, at 1000r/min, 60 DEG C, stirring carries out coprecipitation reaction, until grain diameter is grown to
7 μm, presoma nuclear material is obtained, continues aforesaid operations, sodium hydroxide solution is only replaced with to the sodium carbonate liquor of 1mol/L
PH value for adjusting reaction system is maintained at 9.5, and at 1000r/min, 60 DEG C, stirring carries out coprecipitation reaction, until low nickel
Content nickel cobalt manganese solution and the charging of high nickel content nickel and cobalt solution finish, and obtain the solution containing presoma nucleocapsid layer material；
(2) by the solution containing presoma nucleocapsid layer material obtained by step (1), at 600r/min, 60 DEG C, stirring is aged
10h, filtering, deionized water washing, at 80 DEG C, dry 10h, before obtaining high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material
Drive body Ni0.78Co0.11Mn0.11(OH)2；
(3) in 1g(0.01055mol) the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material presoma of step (2) gained
Ni0.78Co0.11Mn0.11(OH)2In, 0.462g(0.0110mol is added) a hydronium(ion) lithia (elemental lithium and nickel, cobalt, manganese member
The molar ratio of the sum of plain molal quantity is 1.04:1), 6min is ground, is warming up to 450 DEG C with 4 DEG C/min of speed, is pre-sintered 4h, then
750 DEG C are warming up to 4 DEG C/min of speed, 12h is sintered, obtains high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material
LiNi0.78Co0.11Mn0.11O2。
High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention is assembled into battery: being weighed
High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the 0.16 g embodiment of the present invention is added 0.02g acetylene black and leads
Electric agent, 0.02g Kynoar make binder, N-Methyl pyrrolidone as dispersing agent, after mixing, are applied on aluminium foil and make
It is anode with metal lithium sheet in vacuum glove box at negative electrode tab, using the composite membrane of pe, pp as diaphragm, 1mol/L hexafluorophosphoric acid
Lithium/DMC:EC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
As shown in figure 5, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention 2.5~
4.5V, 0.1C(20mA/g) under multiplying power, first discharge specific capacity 199mAh/g.
As shown in fig. 6, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention 2.5~
4.5V, 1C(200mA/g) under multiplying power, first discharge specific capacity 186.5mAh/g, 100 circle of circulation, specific discharge capacity still keeps
In 162mAh/g, capacity retention ratio 86.9%.
As shown in fig. 7, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention 2.5~
4.5V, 0.1C(20mA/g) under multiplying power, first discharge specific capacity 199.2mAh/g, 10 circle of circulation, specific discharge capacity still keeps
In 199.8mAh/g, capacity retention ratio 100.3%；0.5C(100mA/g) under multiplying power, first discharge specific capacity 189.6mAh/
G, 10 circle of circulation, specific discharge capacity remain at 187.9mAh/g, capacity retention ratio 99.1%；1C(200mA/g) under multiplying power,
First discharge specific capacity is 181.2mAh/g, and 10 circle of circulation, specific discharge capacity remains at 178.6mAh/g, and capacity retention ratio is
98.6%；2C(400mA/g) under multiplying power, first discharge specific capacity 173.4mAh/g, circulation 10 is enclosed, and specific discharge capacity is still kept
In 165.8mAh/g, capacity retention ratio 95.6%；5C(1000mA/g) under multiplying power, first discharge specific capacity 159.8mAh/g,
10 circle of circulation, specific discharge capacity remain at 158.6mAh/g, capacity retention ratio 99.2%；10C(2000mA/g) under multiplying power,
First discharge specific capacity is 140mAh/g, and 10 circle of circulation, specific discharge capacity remains at 138.9mAh/g, and capacity retention ratio is
99.2%。
High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material embodiment 2
The chemical formula of the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material are as follows: LiNi0.75Co0.11Mn0.14O2, be by
The core-shell structure particles that the average grain diameter of nickelic just core, middle layer and shell composition is 7.5 μm；It is described it is nickelic just core be
LiNi0.9Co0.1O2, average diameter is 0.8 μm；The middle layer is that mixed lithium is resulting after the agent of nickel cobalt manganese sodium hydroxide pellets is co-precipitated
Nickle cobalt lithium manganate, average thickness are 5.2 μm；The shell is the mixed resulting nickel cobalt of lithium after the co-precipitation of nickel cobalt manganese sodium carbonate precipitating reagent
LiMn2O4, average thickness are 1.5 μm；Nickel element is uniformly distributed in nickelic just core, and is gradually successively decreased since middle layer to shell,
Cobalt element is uniformly distributed in nickelic just core, middle layer and shell, and manganese element is gradually increased since middle layer to shell；It is described nickelic
The molar percentage that nickel in first core accounts for total nickel content is 12~13%；The nickel content nickelic just in core, middle layer or shell,
The percentage for accounting for the sum of each layer nickel, cobalt and manganese total mole number is respectively 93%, < 93~74%, < 74~70%；The manganese content exists
In middle layer or shell, the percentage for accounting for the sum of each layer nickel, cobalt and manganese total mole number is respectively > 0~17%, > 17~20%；It is nickelic
In first core, middle layer or shell, the sum of nickel, cobalt, manganese mole percent are 100%.
Through detecting, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention is pure phase nickel cobalt manganese
Tertiary cathode material.
Through detecting, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention is average grain diameter
7.5 μm of spheric granules, pattern are uniform.
Through detecting, in high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention, nickel element exists
It is uniformly distributed in nickelic just core, and gradually successively decreases since middle layer to shell, cobalt element is equal in nickelic just core, middle layer and shell
Even distribution, manganese element are gradually increased since middle layer to shell；The average diameter of nickelic just core is 0.8 μm, the average thickness in middle layer
Degree is 5.2 μm, and the average thickness of shell is 1.5 μm.
The preparation method embodiment 2 of high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material
(1) by the 2L high nickel content nickel and cobalt solution (mixed solution of nickel nitrate and cobalt nitrate, wherein Ni, Co account for total metal ion
Molar percentage is followed successively by 93%, 7%, concentration of metal ions 2mol/L) with charging rate 90mL/h, be pumped into equipped with 2L,
The volume of 0.4mol/L ammonia spirit is and to stir in the reaction kettle of 5L, after forming 0.8 μm of average grain diameter of nickelic just core, then
By the 2L low nickel content nickel cobalt manganese solution (mixed solution of nickel nitrate, cobalt nitrate and manganese nitrate, wherein Ni, Co, Mn account for total metal
The molar percentage of ion is followed successively by 67%, 13%, 20%, concentration of metal ions 2mol/L) with charging rate 45mL/h, it is pumped into
In high nickel content nickel and cobalt solution, it is mixed, at the same time, will be constantly pumped into the high nickel content nickel of low nickel content nickel cobalt manganese solution
Cobalt liquor is pumped into and has been formed in the nickelic just reaction kettle of the ammonia spirit of core with charging rate 90mL/h, while using mass concentration
The ammonia concn that 25% ammonium hydroxide adjusts reaction system is maintained at 0.4mol/L, adjusts reaction with the sodium hydroxide solution of 5mol/L
The pH value of system is maintained at 10.5, and at 800r/min, 55 DEG C, stirring carries out coprecipitation reaction, until grain diameter grows to 6 μ
M obtains presoma nuclear material, continues aforesaid operations, and sodium hydroxide solution is only replaced with to the sodium carbonate liquor of 1.2mol/L
PH value for adjusting reaction system is maintained at 10, and at 800r/min, 55 DEG C, stirring carries out coprecipitation reaction, until low nickel contains
Amount nickel cobalt manganese solution and the charging of high nickel content nickel and cobalt solution finish, and obtain the solution containing presoma nucleocapsid layer material；
(2) by the solution containing presoma nucleocapsid layer material obtained by step (1), at 600r/min, 60 DEG C, stirring is aged
10h, filtering, deionized water washing, at 80 DEG C, dry 10h, before obtaining high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material
Drive body Ni0.75Co0.11Mn0.14O2(OH)2；
(3) in 1g(0.01078mol) the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material presoma of step (2) gained
Ni0.75Co0.11Mn0.14O2(OH)2In, 0.429g(0.0058mol is added) lithium carbonate (elemental lithium and nickel, cobalt, manganese element molal quantity
The sum of molar ratio be 1.08:1), grind 5min, be warming up to 400 DEG C with 3 DEG C/min of speed, be pre-sintered 5h, then with speed 3
DEG C/min is warming up to 700 DEG C, it is sintered 16h, obtains high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material
LiNi0.75Co0.11Mn0.14O2。
Gained tertiary cathode material is assembled into battery: weighing lithium ion cell positive obtained by the 0.16 g embodiment of the present invention
Material, addition 0.02g acetylene black makees conductive agent and 0.02g Kynoar makees binder, and N-Methyl pyrrolidone is as dispersion
Agent is applied on aluminium foil and negative electrode tab is made after mixing, is anode with metal lithium sheet, with pe, pp in vacuum glove box
Composite membrane is diaphragm, 1mol/L lithium hexafluoro phosphate/DMC:EC(volume ratio 1:1) it is electrolyte, it is assembled into the button electricity of CR2025
Pond.
As shown in figure 8, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention 2.5~
4.5V, 0.1C(20mA/g) under multiplying power, first discharge specific capacity 197mAh/g.
Through detecting, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention in 2.5~4.5V,
1C(200mA/g) under multiplying power, first discharge specific capacity 184.2mAh/g, circulation 100 is enclosed, and specific discharge capacity remains at
160.1mAh/g, capacity retention ratio 86.9%.
Through detecting, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention in 2.5~4.5V,
0.1C(20mA/g) under multiplying power, first discharge specific capacity 197mAh/g, circulation 10 is enclosed, and specific discharge capacity remains at
197.5mAh/g, capacity retention ratio 100.3%；10C(2000mA/g) under multiplying power, first discharge specific capacity 138.6mAh/g,
10 circle of circulation, specific discharge capacity remain at 137.1mAh/g, capacity retention ratio 98.9%.
High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material embodiment 3
The chemical formula of the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material are as follows: LiNi0.79Co0.11Mn0.1O2, it is by height
The core-shell structure particles that the nickel average grain diameter that just core, middle layer and shell form is 7.5 μm；It is described it is nickelic just core be
LiNi0.9Co0.1O2, average diameter is 0.7 μm；The middle layer is that mixed lithium is resulting after nickel cobalt manganese potassium hydroxide precipitating reagent is co-precipitated
Nickle cobalt lithium manganate, average thickness are 5.5 μm；The shell is the mixed resulting nickel cobalt of lithium after the co-precipitation of nickel cobalt manganese potassium carbonate precipitating reagent
LiMn2O4, average thickness are 1.3 μm；Nickel element is uniformly distributed in nickelic just core, and is gradually successively decreased since middle layer to shell,
Cobalt element is uniformly distributed in nickelic just core, middle layer and shell, and manganese element is gradually increased since middle layer to shell；It is described nickelic
The molar percentage that nickel in first core accounts for total nickel content is 14~15%；The nickel content nickelic just in core, middle layer or shell,
The percentage for accounting for the sum of each layer nickel, cobalt and manganese total mole number is respectively 85%, < 85~78%, < 78~75%；The manganese content exists
In middle layer or shell, the percentage for accounting for the sum of each layer nickel, cobalt and manganese total mole number is respectively > 0~12%, > 12~15%；It is nickelic
In first core, middle layer or shell, the sum of nickel, cobalt, manganese mole percent are 100%.
Through detecting, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention is pure phase nickel cobalt manganese
Tertiary cathode material.
Through detecting, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention is average grain diameter
7.5 μm of spheric granules, pattern are uniform.
Through detecting, in high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention, nickel element exists
It is uniformly distributed in nickelic just core, and gradually successively decreases since middle layer to shell, cobalt element is equal in nickelic just core, middle layer and shell
Even distribution, manganese element are gradually increased since middle layer to shell；The average diameter of nickelic just core is 0.7 μm, the average thickness in middle layer
Degree is 5.5 μm, and the average thickness of shell is 1.3 μm.
The preparation method embodiment 3 of high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material
(1) by the 3L high nickel content nickel and cobalt solution (mixed solution of nickel chloride and cobalt chloride, wherein Ni, Co account for total metal ion
Molar percentage is followed successively by 85%, 15%, concentration of metal ions 1.5mol/L) with charging rate 120mL/h, be pumped into equipped with 2L,
The volume of 0.5mol/L ammonia spirit is and to stir in the reaction kettle of 5L, after forming 0.7 μm of average grain diameter of nickelic just core, then
By the 3L low nickel content nickel cobalt manganese solution (mixed solution of nickel chloride, cobalt chloride and manganese chloride, wherein Ni, Co, Mn account for total metal
The molar percentage of ion is followed successively by 75%, 10%, 15%, concentration of metal ions 1.5mol/L) with charging rate 60mL/h, pump
Enter in high nickel content nickel and cobalt solution, is mixed, at the same time, will constantly be pumped into the high nickel content of low nickel content nickel cobalt manganese solution
Nickel and cobalt solution is pumped into and has been formed in the nickelic just reaction kettle of the ammonia spirit of core with charging rate 120mL/h, while dense with quality
The ammonia concn that the ammonium hydroxide of degree 28% adjusts reaction system is maintained at 0.5mol/L, is adjusted with the potassium hydroxide solution of 8mol/L anti-
The pH value of system is answered to be maintained at 11.0, at 800r/min, 55 DEG C, stirring carries out coprecipitation reaction, until grain diameter is grown to
6.2 μm, presoma nuclear material is obtained, continues aforesaid operations, potassium hydroxide solution is only replaced with to the potassium carbonate of 0.8mol/L
The pH value that solution is used to adjust reaction system is maintained at 9, and at 900r/min, 65 DEG C, stirring carries out coprecipitation reaction, until low nickel
Content nickel cobalt manganese solution and the charging of high nickel content nickel and cobalt solution finish, and obtain the solution containing presoma nucleocapsid layer material；
(2) by the solution containing presoma nucleocapsid layer material obtained by step (1), at 600r/min, 60 DEG C, stirring is aged
10h, filtering, deionized water washing, at 80 DEG C, dry 10h, before obtaining high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material
Drive body Ni0.79Co0.11Mn0.1(OH)2；
(3) in 1g(0.01048mol) the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material presoma of step (2) gained
Ni0.79Co0.11Mn0.1(OH)2In, 1.122g(0.011mol is added) (elemental lithium rubs two hydration lithium acetates with nickel, cobalt, manganese element
The molar ratio of the sum of your number is 1.05:1), 8min is ground, 500 DEG C is warming up to 5 DEG C/min of speed, is pre-sintered 3h, then with speed
5 DEG C/min of degree is warming up to 800 DEG C, is sintered 10h, obtains high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material
LiNi0.79Co0.11Mn0.1O2。
Gained tertiary cathode material is assembled into battery: weighing lithium ion cell positive obtained by the 0.16 g embodiment of the present invention
Material, addition 0.02g acetylene black makees conductive agent and 0.02g Kynoar makees binder, and N-Methyl pyrrolidone is as dispersion
Agent is applied on aluminium foil and negative electrode tab is made after mixing, is anode with metal lithium sheet, with pe, pp in vacuum glove box
Composite membrane is diaphragm, 1mol/L lithium hexafluoro phosphate/DMC:EC(volume ratio 1:1) it is electrolyte, it is assembled into the button electricity of CR2025
Pond.
As shown in figure 9, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention 2.5~
4.5V, 0.1C(20mA/g) under multiplying power, first discharge specific capacity 194mAh/g.
Through detecting, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention in 2.5~4.5V,
1C(200mA/g) under multiplying power, first discharge specific capacity 181.2mAh/g, circulation 100 is enclosed, and specific discharge capacity remains at
158.1mAh/g, capacity retention ratio 87.3%.
Through detecting, high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention in 2.5~4.5V,
0.1C(20mA/g) under multiplying power, first discharge specific capacity 194mAh/g, circulation 10 is enclosed, and specific discharge capacity remains at
193.2mAh/g, capacity retention ratio 99.6%；10C(2000mA/g) under multiplying power, first discharge specific capacity 138.1mAh/g,
10 circle of circulation, specific discharge capacity remain at 136.2mAh/g, capacity retention ratio 98.6%.
Claims (10)
1. a kind of high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material, it is characterised in that: its chemical formula are as follows:
LiNixCoyMn(1-x-y)O2, wherein 0.70≤x≤0.85,0.05≤y≤0.20,1-x-y > 0 is by nickelic just core, middle layer
With the core-shell structure particles of shell composition；Nickel element is uniformly distributed in nickelic just core, and is gradually passed since middle layer to shell
Subtract, cobalt element is uniformly distributed in nickelic just core, middle layer and shell, and manganese element is gradually increased since middle layer to shell.
2. high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material according to claim 1, it is characterised in that: described nickelic
The average grain diameter of core-shell structure gradient nickel-cobalt-manganternary ternary anode material is 4~8 μm；The average diameter of the nickelic just core is 0.5
~1.5 μm；The average thickness in the middle layer is 3.0~6.5 μm；The average thickness of the shell is 1~2 μm；It is described nickelic first
Core is LiNi0.9Co0.1O2；The middle layer is the mixed resulting nickle cobalt lithium manganate of lithium after the co-precipitation of nickel cobalt manganese hydroxide precipitating reagent；
The shell is the mixed resulting nickle cobalt lithium manganate of lithium after nickel cobalt manganese carbonate deposition agent co-precipitation；Nickel in the nickelic just core accounts for
The molar percentage of total nickel content is 12~20%；The nickel content nickelic just in core, middle layer or shell, account for each layer nickel, cobalt and
The percentage of the sum of manganese total mole number is 95~70%；The manganese content accounts for each layer nickel, cobalt and manganese and always rubs in middle level or in shell
The percentage of the sum of your number is > 0~20%.
3. a kind of preparation method of high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material as claimed in claim 1 or 2, special
Sign is, comprising the following steps:
(1) high nickel content nickel and cobalt solution is pumped into the reaction kettle equipped with ammonia spirit, and stirred, formation average grain diameter 0.5~
1.5 μm nickelic is pumped into high nickel content nickel and cobalt solution just after core, then by low nickel content nickel cobalt manganese solution, is mixed, with this
Meanwhile the high nickel content nickel and cobalt solution for being constantly pumped into low nickel content nickel cobalt manganese solution is pumped into formed it is nickelic just core ammonium hydroxide it is molten
In the reaction kettle of liquid, at the same with ammonium hydroxide adjust reaction system ammonia concn, with hydroxide precipitant solution adjust reactant
It is pH value, stirring carries out coprecipitation reaction and obtains presoma nuclear material until grain diameter grows to 3~7 μm, continues above-mentioned
Operation, only replaces with the pH value that carbonate deposition agent solution is used to adjust reaction system for hydroxide precipitant solution, stirs
Coprecipitation reaction is carried out, until low nickel content nickel cobalt manganese solution and the charging of high nickel content nickel and cobalt solution finish, is obtained containing presoma core
The solution of Shell Materials；
(2) the solution stirring obtained by step (1) containing presoma nucleocapsid layer material is aged, filters, washs, it is dry, it obtains
High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material presoma；
(3) in the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material presoma obtained by step (2), lithium source is added, grinds,
After pre-burning, sintering obtains high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material.
4. high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material according to claim 3, it is characterised in that: step (1)
In, the high nickel content nickel cobalt manganese solution and constantly be pumped into low nickel content nickel cobalt manganese solution high nickel content nickel and cobalt solution plus
Material speed is 40~120mL/h, and the charging rate of the low nickel content nickel cobalt manganese solution is 20~60mL/h；The high nickel content
In nickel and cobalt solution, the concentration of metal ion is 1~3mol/L, and the molar percentage that Ni accounts for total metal ion is that 70~95%, Co is accounted for
The molar percentage of total metal ion is 5~30%, and Ni, Co ion summation are 100%；In the low nickel content nickel cobalt manganese solution,
The concentration of metal ion is 1~3mol/L, and the molar percentage that Ni accounts for total metal ion is that 60~80%, Co accounts for total metal ion
Molar percentage be the molar ratio that 10~30%, Mn accounts for total metal ion be 10~30%, Ni, Co, Mn ion summation are 100%；
In same reaction system, the nickel content of low nickel content nickel cobalt manganese solution is lower than the nickel content of high nickel content nickel and cobalt solution.
5. according to the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material of claim 3 or 4, it is characterised in that: step
(1) in, the volume ratio of ammonia spirit in reaction kettle, low nickel content nickel cobalt manganese solution and high nickel content nickel and cobalt solution is 0.1~
1.0:0.8~1.2:1；The molar concentration of the ammonia spirit is 0.3~0.5mol/L；It is dense that reaction system ammonium hydroxide is adjusted with ammonium hydroxide
Degree is maintained at 0.3~0.5mol/L；The mass concentration of ammonium hydroxide for adjusting reaction system ammonia concn is 25~28%.
6. the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material according to one of claim 3~5, it is characterised in that:
In step (1), pH value of reaction system is adjusted with hydroxide precipitant solution and is maintained at 10.5~11.5；The hydroxide is heavy
The molar concentration of shallow lake agent solution is 5~10mol/L；The hydroxide precipitating reagent is sodium hydroxide, potassium hydroxide or hydroxide
One or more of lithium.
7. the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material according to one of claim 3~6, it is characterised in that:
In step (1), pH value of reaction system is adjusted with carbonate deposition agent solution and is maintained at 8.5~10.5；The carbonate deposition agent
The molar concentration of solution is 0.5~1.5mol/L；The carbonate deposition agent is sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate
Or one or more of saleratus.
8. the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material according to one of claim 3~7, it is characterised in that:
In step (1), in the coprecipitation reaction for generating presoma nuclear material and generating presoma nucleocapsid layer material, the speed of stirring
It is 600~1200r/min, temperature is 50~70 DEG C；The high nickel content nickel and cobalt solution and low nickel content nickel cobalt manganese solution
For the mixed solution of one or more of soluble nickel salt, soluble cobalt or soluble manganese salt；The soluble nickel salt is
One or more of nickel sulfate, nickel nitrate, nickel acetate or nickel chloride；The soluble cobalt is cobaltous sulfate, cobalt nitrate, acetic acid
One or more of cobalt or cobalt chloride；The solubility manganese salt is one of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride
Or it is several.
9. the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material according to one of claim 3~8, it is characterised in that:
In step (2), the speed of the stirring is 400~800r/min；The temperature of the ageing be 50~80 DEG C, the time be 5~
15h；The temperature of the drying is 50~100 DEG C, and the time is 5~15h.
10. the high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material according to one of claim 3~9, it is characterised in that:
In step (3), nickel in elemental lithium in the lithium source and high nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material presoma,
Cobalt, manganese element the molar ratio of the sum of molal quantity be 1.01~1.08:1；The lithium source be lithium hydroxide, lithium nitrate, lithium carbonate,
One or more of lithium oxalate or lithium acetate and their hydrate；The time of the grinding is 5~10min；It is described pre-
The temperature of burning is 350~550 DEG C, and the time is 3~6h；The temperature of the sintering be 650~950 DEG C, the time be 8~for 24 hours；It is described
The heating rate of pre-burning and sintering is 3~5 DEG C/min.
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