CN108615868A - A kind of sphericity is high and the nickel-cobalt-manganese ternary material precursor and its preparation method and application of the low impurity of surface compact - Google Patents
A kind of sphericity is high and the nickel-cobalt-manganese ternary material precursor and its preparation method and application of the low impurity of surface compact Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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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- 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 discloses a kind of sphericity, high and the low impurity of surface compact nickel-cobalt-manganese ternary material precursor and its preparation method and application, belongs to lithium ion battery preparing technical field.The preparation method of the present invention includes the following steps：Nickel source, cobalt source, the dissolving of manganese source compound are configured to certain density solution in deionized water；Then after prepared solution being mixed with concentrated ammonia liquor, enter in reaction kettle with precipitating reagent, ammonium salt solution cocurrent and reacted；Then by gained presoma slurry through washing, starch again, wash again, then a certain amount of aqueous slkali will be entered during starching；It is last spray-dried, you can to obtain the nickel-cobalt-manganese ternary material precursor of the present invention.It is extremely low that method using the present invention can prepare the impurity content during the better crystallinity degree of gained nickel-cobalt-manganese ternary material precursor, product sphericity be high and surface compact, product, can be used for processability more preferably anode material lithium nickle cobalt manganic acid of lithium ion battery.
Description
Technical field
The invention belongs to lithium ion battery preparing technical fields, more particularly to one kind passing through metal ion under liquid-phase system
Coprecipitation technology prepares nickelic system's nickel-cobalt-manganese ternary material precursor sulfur reduction of sphericity height and surface compact, removal of impurities prepares work
The high nickle cobalt lithium manganate of electro-chemical activity, the anode based on the nickle cobalt lithium manganate can be prepared by this method in skill
Material and include the positive electrode secondary cell.
Background technology
Lithium ion battery because having many advantages, such as that voltage is high, energy density is high, having extended cycle life, due to environmental pollution is small by blueness
It looks at, material of the positive electrode as most critical in current lithium ion battery, its development also most merits attention.Ternary precursor is
The main raw material(s) of ternary material is manufactured, production ternary material needs the ternary precursor using equivalent, ternary precursor current
Account for about the 55% of ternary material cost.Due to presoma quality (pattern, grain size, particle diameter distribution, specific surface area, impurity content,
Tap density etc.) directly determine the physical and chemical index of last sintered product, therefore presoma to the production of ternary material to closing weight
It wants.It can be said that the technology content of ternary material 60% is all inside forerunner's body technology.But positive electrode producer of the country is universal at present
Ignore the production and research and development of ternary material precursor, most of producer is usually all that direct outsourcing presoma is sintered.
Current Li electricity manufacturing enterprises of the country promote towards the nickelic ternary material direction for possessing more height ratio capacity, wherein with
622 types and 811 type nickle cobalt lithium manganate tertiary cathode materials are most commonly seen.Wherein, 622 type nickle cobalt lithium manganate specific capacities are higher than 523
Type, gram volume can reach 160 milliampere hour or more, or even can reach 180 milliampere hour in the case of high voltage, and processing performance
Good, high-energy, internal structure is loose, is easy to be sintered at a lower temperature.Ni contents more height ratio capacity is higher, and Ni contents reach
The importance of 60% or more material gradually shows, and 622 class materials are developed into the emphasis of industry development, and are used in height
On the EV batteries for holding cylinder Notebook Battery and high-energy density.
811 this nickelic based materials have the advantages such as high power capacity, price be low because nickel content, cobalt content are low, mainly answer
Above the aluminum-shell battery of small-sized Fabrication of High Specific Capacitance and high power capacity cylindrical lithium ion battery.Currently, about 811 this nickelic system's materials
Material Japan, South Korea do preferable, and Sumitomo etc enterprise of such as Japan, the producer that the country is done is many, such as bangpu, big China etc, but
Also all in the pilot scale stage, the scale of volume production is smaller for most of enterprise, also needs to wait for the opportunity in market.Therefore, developmental research
Go out to be suitable for the presoma and its preparation process of nickelic system's nickel-cobalt-manganese ternary materials such as above-mentioned 622 and 811 types, and improves gained nickel cobalt
The structure and morphology of manganese ternary material precursor reduces its impurity content, for ensureing the high ni-type nickle cobalt lithium manganate ternary of gained just
The performance of pole material has great importance.
Through retrieval, the patent report about cobalt nickel lithium manganate ternary material forerunner's preparation process has more disclosure.Such as,
Chinese Patent Application No. is 201711219583.7, and invention and created name is a kind of low sodium content sulphur nickel-cobalt-manganese ternary element mixing hydrogen
The preparation method of oxide, the preparation method of the sulphur nickel-cobalt-manganese ternary element mixed hydroxides of this application, includes the following steps：
(1) prepared by raw material；(2) pretreatment of raw material；(3) diluted alkaline is prepared；(4) it is co-precipitated；(5) it is aged；(6) it washs；(7) it dries, wherein
The slurry that has been aged first clarification, venting supernatant naturally, be then added the diluted sodium hydroxide solution of a concentration of 0.5-1% concentration into
Row is sized mixing, and is filtered to slurry using centrifuge after sizing mixing 2 ± 0.5 hours, and dilute sodium hydroxide is used respectively again after filtering drying
Solution and deionized water are washed, and last drying can be obtained low sodium content sulphur nickel-cobalt-manganese ternary element mixed hydroxides,
But the sulfur content that this application prepares gained sulphur nickel-cobalt-manganese ternary element mixed hydroxides is still higher.
Invention content
1. technical problems to be solved by the inivention
It is of the existing technology above insufficient it is an object of the invention to overcome, and provide that a kind of sphericity is high and surface
Nickelic system's nickel-cobalt-manganese ternary material precursor and its preparation method and application of fine and close low impurity.Method using the present invention can be with
It is good that sphericity height, compactness is prepared, and nickelic system's nickel-cobalt-manganese ternary material precursor that impurity content is extremely low, to ensure
The chemical property of nickle cobalt lithium manganate tertiary cathode material.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention is：
First, a kind of sphericity height of the present invention and nickelic system's nickel-cobalt-manganese ternary material forerunner of the low impurity of surface compact
Body, the presoma are the spherical structure of the surface compact of rule, and the content of S is 0.010~0.020wt%, Na in presoma
Content be not more than 100ppm.
Further, the granularity D50 of the granular precursor is 10~15 μm, and tap density is not less than 2.2g/cm3。
Second, a kind of sphericity height of the present invention and nickelic system's nickel-cobalt-manganese ternary material precursor of the low impurity of surface compact
Preparation method, include the following steps：
1) weigh soluble nickel source, cobalt source and manganese source compound, and by nickel source, cobalt source and manganese source compound be dissolved in from
Certain density solution is configured in sub- water；
2) in temperature of reaction system control at 62~78 DEG C, by prepared solution and complexing agent after mixing with it is heavy
Shallow lake agent, ammonium salt solution cocurrent, which enter in reaction kettle, is reacted；
3) most dry through spraying afterwards by reaction gained nickel-cobalt-manganese ternary material precursor slurry through washing, starching again, wash again
It is dry to get high and dense surface low impurity content the nickel-cobalt-manganese ternary material precursor product to sphericity, wherein starching process again
It is middle that a certain amount of aqueous slkali is added.
Further, the added aqueous slkali in the process of starching again of the step 3) is sodium hydroxide, potassium hydroxide and hydrogen-oxygen
One or more in change zinc, the molar concentration of aqueous slkali is 4~5.8mol/L, and the amount for the alkali compounds being added is sample
The 1%~5% of quality.
Further, the solid content for starching solution again is 20%~30%, then starches the time as 1h~2h.
Further, the pH value in reaction kettle is controlled 9~12 in the step 2), waits for that pH value of reaction system is stablized
Afterwards, the reaction was continued 6~12h；The complexing agent is concentrated ammonia liquor, and the dosage of complexing agent is rubbed by nickel, cobalt, manganese Metal ion in solution
The sum of you and NH4 +The ratio between molal quantity be added for 1.0~2.0；The precipitating reagent is sodium hydroxide, potassium hydroxide and hydrogen
It is one or more in zinc oxide, a concentration of 3~6mol/L of precipitating reagent；The ammonium salt is ammonium nitrate, ammonium sulfate, ammonium chloride
With one or more in ammonium phosphate, and the NH of ammonium salt solution4 +A concentration of 2~5mol/L.
Further, in the step 1) soluble nickel source, cobalt source and manganese source compound according to molar ratio Ni/Co/Mn
It is 60:20:20 or 80:10:10 are weighed, before deionized water, nickel source, the 811 type nickel cobalt manganese of weight proportion of cobalt source and manganese source
It is 100 to drive body：(10~70)：(1~10)：(0.5~5), 622 type nickel cobalt manganese presomas are 100：(5~50)：(2~20)：
(1~10)；And in step 1) in 811 type nickel cobalt manganese presoma of acquired solution nickel a concentration of 20~145g/L, cobalt it is a concentration of
2.5~20g/L, a concentration of 2~20g/L of manganese, a concentration of 15~110g/L of nickel in 622 type nickel cobalt manganese presomas, cobalt it is dense
Degree is 5~35g/L, a concentration of 5~35g/L of manganese.
Further, the soluble nickel source compound be nickel sulfate, Nickel Chloride and nickel nitrate in one kind or
A variety of, the soluble cobalt source compound is one or more, the institute in cobalt nitrate, cobaltous sulfate, cobalt oxalate and cobaltous dichloride
The soluble manganese source compound stated is one or more in manganese nitrate, manganese sulfate and manganese chloride.
Further, in ammonium salt solution used in step 2) containing in n-hexane, toluene, ethylbenzene and pentane one kind or
It is a variety of, and in ammonium salt solution organic matter total content by addition ammonium salt solution gross mass 0.01-1%.
Third, the application for nickelic system's nickel-cobalt-manganese ternary material precursor that method using the present invention is prepared, by institute
Nickel-cobalt-manganese ternary material precursor reacts with lithium compound nickle cobalt lithium manganate cell positive material is prepared or will obtain
Nickel-cobalt lithium manganate cathode material be applied to battery in.
3. advantageous effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result：
(1) nickelic system's nickel-cobalt-manganese ternary material precursor of a kind of sphericity of the invention height and the low impurity of surface compact,
The nickel-cobalt-manganese ternary material precursor is the spherical structure of rule, in presoma the content of S be 0.010~0.020wt%, Na
Content is not more than 100ppm, and relative to existing nickel-cobalt-manganese ternary material precursor, impurity content is relatively low, and product purity is high, and
Its sphericity is high, surface soundness is good, and granularity D50 is at 10~15 μm, narrow particle size distribution.
(2) a kind of sphericity of the invention is high and nickelic system's nickel-cobalt-manganese ternary material precursor of the low impurity of surface compact
Preparation process takes complexing agent uniformly to be mixed with reaction raw materials solution, then makees jointly in certain pH value with precipitating reagent, ammonium salt solution
It is final to realize three metal ion species and OH under-High sphericity, dense surface and impurity content is prepared in the technique of co-precipitation
Extremely low nickel-cobalt-manganese ternary material precursor, which is sintered gained nickle cobalt lithium manganate, and there is more preferably electrochemistry to follow
Ring performance and higher specific capacity.
(3) a kind of sphericity of the invention is high and nickelic system's nickel-cobalt-manganese ternary material precursor of the low impurity of surface compact
Preparation process, will reaction gained nickel-cobalt-manganese ternary material precursor slurry washed, starched again, washing process again, and starch place again
Certain aqueous slkali is added during reason, so as to be reduced in products obtained therefrom on the basis of presoma performance obtained by guarantee
Impurity content ensures its follow-up application effect.
(4) a kind of sphericity of the invention is high and nickelic system's nickel-cobalt-manganese ternary material precursor of the low impurity of surface compact
Preparation process, by the amount, concentration of added aqueous slkali in sizing process again, starch again the reaction conditions such as time and reaction temperature into
The stringent control of row, while coordinating with the addition of ammonium salt solution, it is miscellaneous in gained presoma product to be conducive to further decrease
Matter content.
(5) a kind of sphericity of the invention is high and nickelic system's nickel-cobalt-manganese ternary material precursor of the low impurity of surface compact
Preparation process, by adding the organic matter of certain type and content into ammonium salt solution, to help to improve gained presoma
The structure and morphology of product ensures that preparing gained presoma has higher sphericity and consistency, and then is conducive to improve gained
The performance of presoma product.
(6) a kind of sphericity of the invention is high and nickelic system's nickel-cobalt-manganese ternary material precursor of the low impurity of surface compact
Using by the way that safety can be prepared through high-temperature calcination with lithium compound in the persursor material of the present invention and there is high-energy
The nickelic system's nickle cobalt lithium manganate of cell positive material of density, disclosure satisfy that the requirement of electrode for secondary battery active material,
It makes the cell positive material form anode, can get the good large capacity of secure context and good secondary of cycle performance
Battery.
Description of the drawings
Fig. 1 is the SEM figures for the nickel cobalt aluminium hydroxide that embodiment 1 obtains；
Fig. 2 is the SEM figures for the nickel cobalt aluminium hydroxide that comparative example 1 obtains.
Specific implementation mode
To further appreciate that present disclosure, in conjunction with specific embodiment, the present invention is described in detail.
A kind of sphericity height of the present invention and the system of nickelic system's nickel-cobalt-manganese ternary material precursor of the low impurity of surface compact
Standby technique, includes the following steps：1) soluble nickel source, cobalt source and manganese source compound, are weighed, and by nickel source, cobalt source, manganese source chemical combination
Object dissolving is configured to certain density solution in deionized water, solubility nickel source, cobalt when preparing 811 type nickel cobalt manganese presoma
Source and manganese source compound are 80 according to molar ratio Ni/Co/Mn:10:10 are weighed, and control deionized water, nickel source, cobalt source and
The weight proportion of manganese source is 100：(10~70)：(1~10)：(0.5~5), it is soluble when preparing 622 type nickel cobalt manganese presoma
Nickel source, cobalt source and manganese source compound are 60 according to molar ratio Ni/Co/Mn:20:20 are weighed, and control deionized water, nickel
The weight proportion in source, cobalt source and manganese source is 100：(5~50)：(2~20)：(1~10)；2), temperature of reaction system control is 62
At~78 DEG C, by prepared solution and concentrated ammonia liquor by the sum of metallic element mole：NH4 +The ratio that mole ratio is 1.0~2.0
It prepares, after uniform stirring, prepared solution enters the reaction kettle under stirring with precipitating reagent, ammonium salt solution cocurrent
In.PH value control in reaction kettle is 9~12, after pH value of reaction system stabilization, the reaction was continued 6~12h；3) institute will, be reacted
Nickel-cobalt-manganese ternary material precursor slurry through wash, starches again, wash again, then starch process addition alkali compounds, additive amount
It is the 1%~5% of sample quality, then it is 20%~30% to starch the solid content of solution, then starches the time as 1h~2h.Most afterwards through spraying
It is dry to get to the nickel-cobalt-manganese ternary material precursor product of spherical, extremely low impurity content and surface compact.
The soluble nickel source compound of the present invention is solvable to be one or more in nickel sulfate, Nickel Chloride and nickel nitrate
Property cobalt source compound be cobalt nitrate, cobaltous sulfate, cobalt oxalate and cobaltous dichloride in it is one or more, soluble manganese source compound is
It is one or more in manganese nitrate, manganese sulfate and manganese chloride, and nickel in 811 type nickel cobalt manganese presoma of mixed solution obtained by step 1)
The type nickel cobalt manganese presoma of a concentration of 20~145g/L, a concentration of 2.5~20g/L of cobalt, a concentration of 2~20g/L of manganese, 622
A concentration of 15~110g/L of middle nickel, a concentration of 5~35g/L of cobalt, a concentration of 5~35g/L of manganese.The precipitating reagent is hydrogen
It is one or more in sodium oxide molybdena, potassium hydroxide, zinc hydroxide, a concentration of 3~6mol/L of precipitating reagent.The present invention ammonium salt be
It is one or more in ammonium nitrate, ammonium sulfate, ammonium chloride, ammonium phosphate, the concentration (NH of ammonium salt solution4 +Concentration) it is 2~5mol/L,
And the addition of ammonium salt is by the sum of metallic element mole：NH4 +The ratio that mole ratio is 1.0~2.0 is added, ammonium salt solution used
In containing one or more in n-hexane, toluene, ethylbenzene and pentane, and the total content of organic matter is added in ammonium salt solution
Enter the 0.01~1% of ammonium salt solution gross mass.The aqueous slkali being added when starching again is sodium hydroxide, potassium hydroxide, hydroxide
It is one or more in zinc, a concentration of 4~5.8mol/L of aqueous slkali.
The present invention takes complexing agent uniformly to be mixed with reaction raw materials solution, then with precipitating reagent, ammonium salt solution in certain pH value
Collective effect, it is final to realize three metal ion species and OH-The technique of co-precipitation prepares nickel-cobalt-manganese ternary material precursor；Pass through control
The addition speed of precipitating reagent processed, to control the pH value of reaction system；By controlling the addition speed of mixed solution, to control
The proportionate relationship of Ni, Co, Mn tri- kinds of essential elements and precipitating reagent is controlled by the concentration and charging rate that control ammonium salt solution
The granularity and pattern of product, the final control realized to nickel, three kinds of cobalt, manganese essential element coprecipitation process.By washing, again
Slurry is washed and alkaline solution is added during starching again adjust and washes and reaction process raisings reaction temperature appropriate, instead again
Should during a certain amount of ammonium salt solution be added, be finally reached sulfur reduction, the purpose of removal of impurities, be made sphericity high and surface compact,
The extremely low nickel-cobalt-manganese ternary material precursor of impurity content.
To further appreciate that present disclosure, in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Ni/Co/Mn is 80 in molar ratio:10:10 weigh nickel chloride 150.0g, cobalt chloride 17.8g, manganese chloride 9.9g, and
By nickel chloride, cobalt chloride, manganese chloride dissolving be configured in deionized water total concentration of metal ions be 1.8mol/L mixing it is molten
Liquid；By the sum of metallic element molal quantity and NH4 +Mole ratio is 1.0 concentrated ammonia liquors for being added that mass fraction is 25% to mixed solution
59.1mL；Temperature of reaction system controls at 65 DEG C, and the NaOH of prepared solution and prepared precipitating reagent 6mol/L is molten
Liquid, 2.0mol/L ammonium chloride solution (contain n-hexane in ammonium salt solution used, and is ammonium salt is added in the total content of n-hexane
The 1% of solution gross mass) cocurrent enters in the reaction kettle under the stirring, the pH value in reaction kettle controlled 11.5；
After pH value of reaction system stabilization, the reaction was continued 8h；Then by acquired nickel-cobalt-manganese ternary material precursor slurry through washing, again
Slurry is washed again, then it is 20% to starch the solid content of solution, then the NaOH solution 15.0mL of 5.8mol/L is added during starching, then is starched
Stirring adjusts and washes 2h；It is last spray-dried to get to before the nickel-cobalt-manganese ternary material of spherical, extremely low impurity content and surface compact
Drive body Ni0.8Co0.1Mn0.1(OH)2Product, as shown in Figure 1.Sample after spray drying detects its sulfur content through infrared C-S analyzer and is
0.012%, it is 58.7ppm that sample detects its Na content through ICP.
Comparative example 1
Ni/Co/Mn is 80 in molar ratio:10:10 weigh nickel chloride 150.0g, cobalt chloride 17.8g, manganese chloride 9.9g, and
By nickel chloride, cobalt chloride, manganese chloride dissolving be configured in deionized water total concentration of metal ions be 1.8mol/L mixing it is molten
Liquid；It is 25% by the NaOH solution of prepared mixed solution and prepared precipitating reagent 5.8mol/L, complexing agent mass fraction
Concentrated ammonia liquor 59.1mL cocurrents enter in the reaction kettle under the stirring, temperature of reaction system controls at 65 DEG C, will be anti-
The pH value in kettle is answered to control 11.5；After pH value of reaction system stabilization, the reaction was continued 8h；Then by acquired nickel-cobalt-manganese ternary
Material precursor slurry cooled to room temperature obtains nickel-cobalt-manganese ternary material precursor through washing, filtering, drying
Ni0.8Co0.1Mn0.1(OH)2Product, pattern are shown in Figure 2.Sample after drying detects its sulfur content through infrared C-S analyzer
It is 0.550%, it is 430ppm that sample detects its Na content through ICP.
Embodiment 2
Ni/Co/Mn is 60 in molar ratio:20:20 weigh nickel chloride 150.0g, cobalt chloride 50.1g, manganese chloride 26.5g, and
Nickel chloride, cobalt chloride, manganese chloride dissolving are configured to the mixed solution of total concentration of metal ions 2mol/L in deionized water；It presses
The sum of metallic element mole and NH4 +Mole ratio is the 1.0 ammonium hydroxide 78.76mL for being added that mass fraction is 25% to mixed solution；
Temperature of reaction system controls at 70 DEG C, by the KOH solution of prepared solution and prepared precipitating reagent 6mol/L, 3.0
Mol/L ammonium chloride solution (contain toluene in ammonium salt solution used, and in ammonium salt solution toluene total content by ammonium salt is added
The 0.5% of solution gross mass) cocurrent enters in the reaction kettle under the stirring, the pH value control in reaction kettle existed
11.4；After pH value of reaction system stabilization, the reaction was continued 7h；Then by acquired nickel cobalt aluminium ternary material precursor slurry through water
It washes, starch again, wash again, then it is 25% to starch the solid content of solution, then the KOH solution 6.4mL of 5.8mol/L is added during starching, then
Slurry stirring, which is adjusted, washes 1.5h；It is last spray-dried to get to the nickel-cobalt-manganese ternary material of spherical, extremely low impurity content and dense surface
Material precursor Ni0.6Co0.2Mn0.2(OH)2Product.It is 0.015% that sample after spray drying detects its sulfur content through infrared C-S analyzer,
It is 67.2ppm that sample detects its Na content through ICP.
Embodiment 3
Ni/Co/Mn is 80 in molar ratio:10:10 weigh nickel nitrate 150.0g, cobalt nitrate 18.8g, manganese nitrate 8.7g, and
By nickel nitrate, cobalt nitrate, manganese nitrate dissolving be configured in deionized water total concentration of metal ions be 1.5mol/L mixing it is molten
Liquid；By the sum of metallic element mole and NH4 +Mole ratio is 2.0 ammonium hydroxide 24.1 for being added that mass fraction is 25% to mixed solution
mL；Temperature of reaction system controls at 62 DEG C, by the NaOH solution of prepared solution and prepared precipitating reagent 6mol/L,
2.5mol/L ammonium nitrate solution (contain ethylbenzene in ammonium salt solution used, and in ammonium salt solution ethylbenzene total content to be added
The 0.01% of ammonium salt solution gross mass) cocurrent enters in the reaction kettle under the stirring, the pH value in reaction kettle controlled
11.2；After pH value of reaction system stabilization, the reaction was continued 7h；Then acquired nickel-cobalt-manganese ternary material precursor slurry is passed through
It washes, starches, washes again again, then it is 30% to starch the solid content of solution, then the NaOH solution of 5.8mol/L is added during starching
19.5mL, then starch stirring tune and wash 1.5h；It is last spray-dried to get to the nickel-cobalt-manganese ternary material of spherical, extremely low impurity content
Material precursor Ni0.8Co0.1Mn0.1(OH)2Product.It is 0.017% that sample after spray drying detects its sulfur content through infrared C-S analyzer,
It is 77.3ppm that sample detects its Na content through ICP.
Embodiment 4
Ni/Co/Al is 60 in molar ratio:20:20 weigh nickel sulfate 150.0g, cobaltous sulfate 53.5g, manganese sulfate 32.2g, and
By nickel sulfate, cobaltous sulfate, manganese sulfate dissolving be configured in deionized water total concentration of metal ions be 2.0mol/L mixing it is molten
Liquid；By the sum of metallic element mole and NH4 +Mole ratio is 1.0 ammonium hydroxide 71.2 for being added that mass fraction is 25% to mixed solution
mL；Temperature of reaction system controls at 68 DEG C, by the NaOH solution of prepared solution and prepared precipitating reagent 6mol/L,
The ammonium sulfate of 2.0mol/L (contains pentane, and the total content of pentane is institute in ammonium salt solution in ammonium salt solution used
It is added the 0.7% of ammonium salt solution gross mass) cocurrent enters in the reaction kettle under the stirring, by the pH value control in reaction kettle
System is 10.8；After pH value of reaction system stabilization, the reaction was continued 10h；Then by acquired nickel-cobalt-manganese ternary material precursor material
Slurry is through wash, starch again, wash again, then it is 25% to starch the solid content of solution, then during starching addition 5.8mol/L NaOH solution
13.5mL, then starch stirring tune and wash 2h；It is last spray-dried to get to the nickel-cobalt-manganese ternary material of spherical, extremely low impurity content
Presoma Ni0.6Co0.2Mn0.2(OH)2Product.Sample after spray drying detects its sulfur content through infrared C-S analyzer and is
0.018%, it is 85.6ppm that sample detects its Na content through ICP.
Embodiment 5
Ni/Co/Al is 60 in molar ratio:20:20 weigh nickel sulfate 150.0g, cobalt oxalate, manganese sulfate, and by nickel sulfate,
Cobalt oxalate, manganese sulfate dissolving are configured to the mixed solution that total concentration of metal ions is 1.7mol/L in deionized water；By metal
The sum of element mole and NH4 +Mole ratio is 1.6 ammonium hydroxide for being added that mass fraction is 28% to mixed solution；Temperature of reaction system
Control is at 78 DEG C, by the Zn (OH) of prepared solution and prepared precipitating reagent 3mol/L2The phosphoric acid of solution, 1.6mol/L
Ammonium salt solution (contains n-hexane and toluene, and the total content of n-hexane and toluene is added in ammonium salt solution in ammonium salt solution used
Entering the 0.1% of ammonium salt solution gross mass) cocurrent enters in the reaction kettle under the stirring, the pH value in reaction kettle controlled
12；After pH value of reaction system stabilization, the reaction was continued 12h；Then acquired nickel-cobalt-manganese ternary material precursor slurry is passed through
It washes, starches, washes again again, then it is 27% to starch the solid content of solution, then the Zn (OH) of 4mol/L is added during starching2Solution
20mL, then starch stirring tune and wash 1h；It is last spray-dried to get to before the nickel-cobalt-manganese ternary material of spherical, extremely low impurity content
Drive body Ni0.6Co0.2Mn0.2(OH)2Product.
Embodiment 6
Ni/Co/Mn is 80 in molar ratio:10:10 weigh nickel chloride 150.0g, cobalt chloride 17.8g, manganese chloride 9.9g, and
By nickel chloride, cobalt chloride, manganese chloride dissolving be configured in deionized water total concentration of metal ions be 1.8mol/L mixing it is molten
Liquid；By the sum of metallic element mole and NH4 +Mole ratio is 1.8 ammonium hydroxide for being added that mass fraction is 28% to mixed solution；Instead
Answer system temperature control at 70 DEG C, by the NaOH solution of prepared solution and prepared precipitating reagent 4.5mol/L, 5mol/
The ammonium chloride solution of L (contains n-hexane, ethylbenzene and pentane, and organic matter always contains in ammonium salt solution in ammonium salt solution used
Amount for institute addition ammonium salt solution gross mass 0.85%) cocurrent into be in stirring under reaction kettle in, will be in reaction kettle
PH values control 9；After pH value of reaction system stabilization, the reaction was continued 6h；Then by acquired nickel-cobalt-manganese ternary material forerunner
Body slurry is through washing, starch again, wash again, then it is 25% to starch the solid content of solution, then be added during starching 5mol/L NaOH it is molten
Liquid 15.8mL, then starch stirring tune and wash 1.7h；It is last spray-dried to get to the nickel-cobalt-manganese ternary of spherical, extremely low impurity content
Material precursor Ni0.8Co0.1Mn0.1(OH)2。
1-6 and comparative example 1 are it is found that sphericity height, surface can be prepared in method using the present invention in conjunction with the embodiments
Compactness is good and the lower nickel-cobalt-manganese ternary material precursor of impurity content, and the presoma and lithium compound are carried out high-temperature calcination
Safety and the nickle cobalt lithium manganate cell positive material with high-energy density can be prepared, disclosure satisfy that secondary cell electricity consumption
The requirement of pole active material makes the cell positive material form anode, and it is good big to can get secure context
Capacity and the good secondary cell of cycle performance.
Claims (10)
1. nickelic system's nickel-cobalt-manganese ternary material precursor of a kind of sphericity height and the low impurity of surface compact, it is characterised in that：It should
Presoma is the spherical structure of the surface compact of rule, and the content of S is the content of 0.010~0.020wt%, Na in presoma
No more than 100ppm.
2. before a kind of sphericity height according to claim 1 and nickelic system's nickel-cobalt-manganese ternary material of the low impurity of surface compact
Drive body, it is characterised in that：The granularity D50 of the granular precursor is 10~15 μm, and tap density is not less than 2.2g/cm3。
3. nickelic system's nickel-cobalt-manganese ternary material of a kind of sphericity height as claimed in claim 1 or 2 and the low impurity of surface compact
The preparation method of presoma, which is characterized in that include the following steps：
1) soluble nickel source, cobalt source and manganese source compound are weighed, and nickel source, cobalt source and manganese source compound are dissolved in deionized water
In be configured to certain density solution；
2) in temperature of reaction system control at 62~78 DEG C, by prepared solution and complexing agent after mixing with precipitation
Agent, ammonium salt solution cocurrent, which enter in reaction kettle, is reacted；
3) last spray-dried by reaction gained nickel-cobalt-manganese ternary material precursor slurry through washing, starching again, wash again, i.e.,
The nickel-cobalt-manganese ternary material precursor product of sphericity height and dense surface, extremely low impurity content is obtained, wherein during starching again
A certain amount of aqueous slkali is added.
4. before a kind of sphericity height according to claim 3 and nickelic system's nickel-cobalt-manganese ternary material of the low impurity of surface compact
Drive the preparation method of body, it is characterised in that：The added aqueous slkali in the process of starching again of the step 3) is sodium hydroxide, potassium hydroxide
With it is one or more in zinc hydroxide, the molar concentration of aqueous slkali is 4~5.8mol/L, and the amount for the alkali compounds being added
It is the 1%~5% of sample quality.
5. before a kind of sphericity height according to claim 4 and nickelic system's nickel-cobalt-manganese ternary material of the low impurity of surface compact
Drive the preparation method of body, it is characterised in that：The solid content for starching solution again is 20%~30%, then starches the time as 1h~2h.
6. nickelic system's nickel cobalt manganese of a kind of sphericity height and the low impurity of surface compact according to any one of claim 3-5
The preparation method of ternary material precursor, it is characterised in that：By the pH value control in reaction kettle 9~12 in the step 2),
After pH value of reaction system stabilization, the reaction was continued 6~12h；The complexing agent is concentrated ammonia liquor, and the dosage of complexing agent is by solution
The sum of nickel, cobalt, manganese Metal ion mole and NH4 +The ratio between molal quantity be added for 1.0~2.0；The precipitating reagent is hydrogen
It is one or more in sodium oxide molybdena, potassium hydroxide and zinc hydroxide, a concentration of 3~6mol/L of precipitating reagent；The ammonium salt is
It is one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium phosphate, and the NH of ammonium salt solution4 +A concentration of 2~5mol/L.
7. nickelic system's nickel cobalt manganese of a kind of sphericity height and the low impurity of surface compact according to any one of claim 3-5
The preparation method of ternary material precursor, it is characterised in that：Soluble nickel source, cobalt source and manganese source compound are pressed in the step 1)
It is 60 according to molar ratio Ni/Co/Mn:20:20 or 80:10:10 are weighed, and deionized water, nickel source, the weight of cobalt source and manganese source are matched
It is 100 than 811 type nickel cobalt manganese presomas：(10~70)：(1~10)：(0.5~5), 622 type nickel cobalt manganese presomas are 100：(5
~50)：(2~20)：(1~10)；And in step 1) in 811 type nickel cobalt manganese presoma of acquired solution nickel a concentration of 20~
145g/L, a concentration of 2.5~20g/L of cobalt, a concentration of 2~20g/L of manganese, nickel is a concentration of in 622 type nickel cobalt manganese presomas
15~110g/L, a concentration of 5~35g/L of cobalt, a concentration of 5~35g/L of manganese.
8. nickelic system's nickel cobalt manganese of a kind of sphericity height and the low impurity of surface compact according to any one of claim 3-5
The preparation method of ternary material precursor, it is characterised in that：The soluble nickel source compound be nickel sulfate, Nickel Chloride and
One or more in nickel nitrate, the soluble cobalt source compound is in cobalt nitrate, cobaltous sulfate, cobalt oxalate and cobaltous dichloride
It is one or more, the soluble manganese source compound is one or more in manganese nitrate, manganese sulfate and manganese chloride.
9. high according to a kind of sphericity of the claim according to any one of claim 3-5 and the low impurity of surface compact
The preparation method of nickelic system's nickel-cobalt-manganese ternary material precursor, it is characterised in that：In ammonium salt solution used in step 2) containing just oneself
It is one or more in alkane, toluene, ethylbenzene and pentane, and in ammonium salt solution organic matter total content by ammonium salt solution is added
The 0.01~1% of gross mass.
10. before nickelic system's nickel-cobalt-manganese ternary material that a kind of method using described in any one of claim 3-9 is prepared
Drive the application of body, it is characterised in that：Gained nickel-cobalt-manganese ternary material precursor is reacted with lithium compound, nickel cobalt manganese is prepared
Obtained nickel-cobalt lithium manganate cathode material is applied in battery by acid lithium battery positive electrode.
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