CN104332622B - High-purity, high crystalline spherical nickel cobalt manganese persursor material and preparation method thereof - Google Patents
High-purity, high crystalline spherical nickel cobalt manganese persursor material and preparation method thereof Download PDFInfo
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- CN104332622B CN104332622B CN201410452085.7A CN201410452085A CN104332622B CN 104332622 B CN104332622 B CN 104332622B CN 201410452085 A CN201410452085 A CN 201410452085A CN 104332622 B CN104332622 B CN 104332622B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of high-purity, high crystalline spherical nickel cobalt manganese persursor material, its chemical molecular formula is Ni1‑x‑ yCoxMny(OH)2, wherein the ＜ y ＜ 1 of 0 ＜ x ＜ 1,0；Mass fraction≤0.012% of sodium impurity content therein, mass fraction≤0.30% of sulfate radical foreign matter content, it has high crystalline, intensity >=1100 of characteristic peak 001 in XRD spectrum sign.At least one step employs anti-oxidation measure in the preparation method of nickel cobalt manganese persursor material of the present invention, including raw material preparation process, co-precipitation step and ripening step, raw material preparation process, co-precipitation step and ripening step.The present invention product impurity content is low, good crystallinity, technological process is simple, it is excellent that continuous production, product with stable quality can be achieved.
Description
Technical field
Before anode material of lithium battery technical field, more particularly to a kind of anode material of lithium battery nickel cobalt manganese
Drive body material and preparation method thereof.
Background technology
Lithium ion battery as a kind of novel green secondary cell, with specific capacity it is big, have extended cycle life, self discharge is small,
The advantages of light weight, memory-less effect.Various mobile electronic products (such as mobile phone, camera, notebook are widely used at present
Computer etc.), artificial satellite, the field such as space flight and aviation, before also having good application in the field such as electric automobile and battery-operated motor cycle
Scape.For adapt to these application fields it is growing the need for, to the lithium ion secondary that capacity is bigger, weight is lighter, smaller
The demand of battery constantly increases, therefore, and the specific capacity performance to anode material for lithium-ion batteries proposes higher and higher want
Ask.
Anode material for lithium-ion batteries in the market mainly has cobalt acid lithium, nickle cobalt lithium manganate, LiMn2O4 and ferric phosphate
Lithium four major classes of series.Nickle cobalt lithium manganate can adjust nickel in presoma, cobalt, the ratio of manganese and meet the difference in functionality need of material
Ask, so its application is more and more extensive, used in terms of digital product, energy storage and power.Nickel cobalt manganese hydroxide, i.e.,
Nickel cobalt manganese presoma is the raw material for producing nickle cobalt lithium manganate, and particle size, pattern, the structure of nickel cobalt manganese presoma add to follow-up
Nickle cobalt lithium manganate size, pattern, the structure of work have direct influence.Therefore the quality of nickel cobalt manganese presoma directly determines nickel cobalt
The quality of LiMn2O4.
At present, it is control crystalline hydroxides coprecipitation to prepare the common method of nickel cobalt manganese hydroxide, will be mixed
Metal salt solution obtained in the presence of complexing agent with sodium hydroxide pellets mixed metal hydroxides precipitation.However, this is common
In the course of reaction of the precipitation method, being stirred vigorously and reactor in a small amount of oxygen and precipitation process due to existing in solution
The problems such as sealing is not tight so that cobalt manganese has more or less oxidation in precipitation process, and then causes nickel cobalt manganese to be co-precipitated
Effect is poor, obtains the sediment of sepia, and the product impurity content is high, and crystallinity is poor so that homogeneity of product is not high, and this enters
One step have impact on the performance of following process battery material.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention with defect that there is provided one in background above technology
Kind impurity content is low, good crystallinity high-purity, high crystalline spherical nickel cobalt manganese persursor material, correspondingly provides a kind of work
Skill flow is simple, automaticity is high, the excellent spherical nickel cobalt manganese presoma of continuous production, product with stable quality can be achieved
The preparation method of material.
In order to solve the above technical problems, technical scheme proposed by the present invention is a kind of high-purity, high crystalline spherical nickel
Cobalt manganese persursor material, the chemical molecular formula of the nickel cobalt manganese persursor material is Ni1-x-yCoxMny(OH)2, wherein 0 ＜ x ＜ 1,
0 ＜ y ＜ 1；Mass fraction≤0.012% of sodium impurity content in the nickel cobalt manganese persursor material, sulfate radical foreign matter content
Mass fraction≤0.30%, the nickel cobalt manganese persursor material has high crystalline, its characteristic peak in XRD spectrum sign
001 intensity >=1100.
As a total technical concept, the present invention also provides a kind of preparation side of above-mentioned nickel cobalt manganese persursor material
Method, including raw material preparation process, co-precipitation step and ripening step, the raw material preparation process, co-precipitation step and old
Change at least one step in process step and employ anti-oxidation measure.
In above-mentioned preparation method, it is preferred that the anti-oxidation measure in the raw material preparation process includes：By subsequent step
Need the various raw materials used, reagent to be purchased respectively in material solution form, form plurality of raw materials solution, and it is molten in plurality of raw materials
At least one of liquid adds reducing agent.Our research indicate that, due to there is a small amount of dissolved oxygen in each material solution, these
Although the content of dissolved oxygen is not high, but if material impact can be produced to the quality of product by entering in subsequent reactions system, and
And the removal of this dissolved oxygen is can not to be resolved by leading to inert protective gas into material solution, because inert gas
Being passed through can only prevent the oxygen increment in air to be added in material solution, and could only be removed by adding specific reducing agent
Dissolved oxygen storage in each material solution.
In above-mentioned preparation method, it is preferred that the reducing agent is one kind in hydrazine hydrate, sodium sulfite, nitrite
Or in several mixtures, and each material solution reducing agent addition for material solution volume fraction 0.01%~
1%.
In above-mentioned preparation method, it is preferred that the plurality of raw materials solution include precipitant solution, enveloping agent solution and by
Nickel salt, cobalt salt, manganese salt prepare the mixing salt solution to be formed, and the mixing salt solution is according in standby nickle cobalt lithium manganate of drawing up
Nickel, cobalt, the mol ratio of three kinds of elements of manganese are prepared.It is furthermore preferred that the addition of reducing agent is precipitant solution volume fraction
0.02%~0.06%, the addition of reducing agent is the 0.02%~0.06% of enveloping agent solution volume fraction, reducing agent
Addition is the 0.02%~0.08% of mixing salt solution volume fraction.
In above-mentioned preparation method, it is preferred that the nickel salt, cobalt salt, manganese salt are nickel in sulfate, and mixing salt solution
The total concentration of three kinds of elements of cobalt manganese is controlled at 60~120g/L (more preferably 80~120g/L)；The precipitant solution is hydroxide
Sodium water solution, its concentration control is 80~200g/L (more preferably 80~150g/L)；The enveloping agent solution is ammoniacal liquor, its concentration
Control as 5~100g/L (more preferably 7~50g/L).
In above-mentioned preparation method, it is furthermore preferred that the reaction bottom liquid in follow-up co-precipitation step is sodium hydroxide, ammoniacal liquor
With the mixed solution of reducing agent.The initial pH value of reaction bottom liquid is preferably controlled in 10.2~10.6, reaction bottom liquid
Initial temperature is preferably 45 DEG C~55 DEG C, and the initial concentration of ammonia is preferably controlled in 7g/L~22g/L in reaction bottom liquid.
Although the precipitation reaction kettle in existing other application field, which also has to mention, uses some basic seal approach (examples
As only set sealing ring) and be passed through in inert gas shielding, but existing process and do not recognize that the sealed importance of oxygen barrier, this
Often lead to seal approach and inert gas shielding measure is not comprehensive, it is also not strict enough, finally still have influence on product
Quality, therefore in above-mentioned preparation method, it is preferred that the anti-oxidation measure in the co-precipitation step is included in following measures
At least one of：
(1) thorough seal processing is carried out to precipitation reaction kettle；
(2) it is continually fed into inert gas (preferably nitrogen) before coprecipitation reaction and in course of reaction and is protected, and is sinking
Inert atmosphere is set to maintain certain normal pressure in the inner chamber of shallow lake reactor, to ensure that precipitation environment is in complete anaerobic state.
In above-mentioned preparation method, it is furthermore preferred that the measure of thorough seal processing includes：
(1) water seal is carried out while to the agitating shaft progress mechanical seal of precipitation reaction kettle；
(2) to being connected and sealed between the cell body and groove lid of precipitation reaction kettle by seal washer；
(3) discharge pipe of precipitation reaction kettle is inserted in water and carries out water seal.
In above-mentioned preparation method, it is preferred that during the coprecipitation reaction, the rotating speed of reactor is controlled in 160r/
The temperature control of reaction system is at 45 DEG C~55 DEG C in min~230r/min, course of reaction, the concentration control of ammonia in reaction system
For 10g/L~40g/L, the overall control of solid matter is 150g/L~250g/L in reaction system.
In above-mentioned preparation method, it is preferred that the anti-oxidation measure in the ripening step includes：Coprecipitation reaction
Slurry afterwards is pumped into washing press and carried out after ageing reaction, is pumped directly into without separation of solid and liquid in pure water after washes clean
Drying.
In above-mentioned preparation method, it is preferred that be to use 5wt%~20wt% (more preferably in the ripening step
10wt%~15wt%) alkali lye (preferably sodium hydroxide solution or potassium hydroxide solution) to slurry carry out ageing reaction, ageing
Reaction temperature is 40 DEG C~80 DEG C (more preferably 40 DEG C~60 DEG C), and the ageing reaction time is 30min~60min；It is anti-by ageing
Should after reaction mass be to be washed at normal temperatures using deionized water, and wash to pH value as after 7.5~8.5, after washing
Dried up, dried, drying temperature is preferably 90 DEG C~130 DEG C.
In the technical scheme of the invention described above, the anti-oxidation processing of links in whole technical process is especially highlighted, because
For our experiences show that, links carry out tight anti-oxidation measure, for the lifting of properties of product and quality, especially
Purity and crystalline improvement have highly important meaning.Therefore, most preferred scheme is certainly in the above-mentioned technical solutions
Links all strictly handled according to every anti-oxidation measure of the present invention, including：Each raw material before preparation is molten
Liquid takes above-mentioned corresponding anti-oxidation measure by deoxygenation process in co-precipitation step and ripening step, and
Anti-oxidation measure in co-precipitation step not only includes carrying out precipitation reaction kettle thorough seal processing, and including co-precipitation
Before reaction and it is continually fed into inert gas in course of reaction to be protected, and inert atmosphere is tieed up in the inner chamber of precipitation reaction kettle
Hold certain normal pressure and protective layer.By the integrated use of above-mentioned every anti-oxidation measure, it ensure that in course of reaction and react
Environment almost completely cuts off completely with outside air in kettle, prevents the oxidation of cobalt manganese, it is ensured that the uniform co-precipitation of nickel cobalt manganese.It is same with this
When, corresponding anti-oxidation measure is also taken during the ripening of reaction mass, it is ensured that slurry before non-washes clean not
With air contact.
Compared with prior art, the advantage of above-mentioned technical proposal of the present invention is：
The present invention carries out coprecipitation reaction using continuation mode, and technological process is simple, and solution first is carried out into deoxygenation before reaction
Processing, while carrying out encapsulation process to reactor, prevents cobalt, manganese from entering after reaction system to be oxidized generation high price compound, has
Effect control manganese element and nickel, the coprecipitation reaction process of cobalt element, so that nickel cobalt manganese can equably carry out coprecipitation reaction,
Slurry is protected in ageing process, so as to finally prepare before the spherical nickel cobalt manganese that crystallinity is high, impurity content is few
Drive body material.
In general, it is of the invention compared with existing dry method or other wet processings, the present invention can make manganese element and nickel,
Cobalt element formation is equably co-precipitated, and prepares intensity >=1100 of characteristic peak 001, sodium impurity content during good crystallinity, XRD are characterized
≤ 0.012%, sulfate radical foreign matter content≤0.30%, tap density >=2.20g/cm3Nickel cobalt manganese persursor material；The present invention
Preparation method not only technological process is simple, automaticity is high, and can realize continuous production, it is product with stable quality, excellent
It is different.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the XRD for the spherical nickel cobalt manganese persursor material that the embodiment of the present invention 1 is prepared.
Fig. 2 is the scanning electron microscope (SEM) photograph for the spherical nickel cobalt manganese persursor material that the embodiment of the present invention 1 is prepared.
Embodiment
The embodiment of the present invention is as follows：
A kind of high-purity, high crystalline spherical nickel cobalt manganese persursor material, the chemical molecular of nickel cobalt manganese persursor material
Formula is Ni1-x-yCoxMny(OH)2, wherein the ＜ y ＜ 1 of 0 ＜ x ＜ 1,0；Sodium impurity content in nickel cobalt manganese persursor material≤
0.012%, sulfate radical foreign matter content≤0.30%, nickel cobalt manganese persursor material has characteristic peak in high crystalline, XRD signs
001 intensity >=1100.
The preparation method of the spherical nickel cobalt manganese persursor material of the present invention, comprises the following steps：
(1) raw material prepares：First nickel salt, cobalt salt, manganese salt are prepared to form mixing salt solution, nickel cobalt manganese three in mixing salt solution
The total concentration for planting element is controlled in 80~120g/L；Then by nickel cobalt manganese salt solution be well mixed with reducing agent mixed liquor A (also
The addition of former agent for mixing salt solution volume fraction 0.02%~0.08%)；It is again that 80~150g/L sodium hydroxide is molten
Liquid and reducing agent it is well mixed mixed liquid B (addition of reducing agent for sodium hydroxide solution volume fraction 0.02%~
0.06%)；By 7~50g/L ammoniacal liquor and reducing agent it is well mixed mixed liquor C (addition of reducing agent is that sodium hydroxide is molten
The 0.02% of liquid fraction~0.06%)；Reducing agent is one or more of mixed in hydrazine water, sodium sulfite, nitrite
Compound；
(2) it is co-precipitated：The mixed liquor A of above-mentioned preparation, mixed liquid B and mixed liquor C together cocurrent are added to one equipped with anti-
Answer bottom liquid and the coprecipitation reaction of progress continous way in the precipitation reaction kettle of (seal is good) is handled through thorough seal, react bottom
Liquid is the mixed solution of sodium hydroxide, ammoniacal liquor and reducing agent, and the initial pH value control of reaction bottom liquid reacts bottom 10.2~10.6
The initial temperature of liquid is 45 DEG C~55 DEG C, and the initial concentration of ammonia is controlled in 7g/L~22g/L in reaction bottom liquid；In course of reaction
Constantly it is passed through nitrogen to be protected, and inert atmosphere is maintained certain normal pressure in the inner chamber of precipitation reaction kettle, ensures to sink
Shallow lake environment is in complete anaerobic state；PH value control in course of reaction is 10.5~11.5, and the rotating speed control of reactor exists
160r/min~230r/min, the temperature control of reaction system is at 45 DEG C~55 DEG C, and the concentration control of ammonia is in reaction system
The overall control of solid matter is 150g/L~250g/L in 10g/L~40g/L, reaction system, has been reacted until raw material is stable
Entirely；
The measure of thorough seal processing includes：Enter water-filling while carrying out mechanical seal to the agitating shaft of precipitation reaction kettle
Envelope；To being connected and sealed between the cell body and groove lid of precipitation reaction kettle by seal washer；By the discharge nozzle of precipitation reaction kettle
Water seal is carried out in road insertion water；
(3) it is aged：Ageing reaction, ripening are carried out to the slurry continuously overflowed from precipitation reaction kettle after stable reaction
It is that slurry is carried out to be aged instead using 10wt%~15wt% alkali lye (sodium hydroxide solution or potassium hydroxide solution) in step
Should, ageing reaction temperature is 40 DEG C~60 DEG C, and the ageing reaction time is 30min~60min, by being aged reacted reactant
Material is to be pumped directly into deionized water to be washed at normal temperatures without separation of solid and liquid, and it is 7.5~8.5 to wash to pH value
Afterwards, dried up, dried after washes clean in pure water, drying temperature is 90 DEG C~130 DEG C, and lithium ion battery is being obtained after drying just
The spherical nickel cobalt manganese persursor material that impurity content is low, crystallinity is high of pole material.
For the ease of understanding the present invention, more complete is made to the present invention below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, instrument and equipment used in the present invention etc. can be by city
Field is commercially available or can prepared by existing method.
Embodiment 1：
A kind of high-purity, high crystalline spherical nickel cobalt manganese persursor material of the present invention as shown in Figure 1 and Figure 2, nickel cobalt manganese
The chemical molecular formula of persursor material is Ni1-x-yCoxMny(OH)2, wherein the ＜ y ＜ 1 of 0 ＜ x ＜ 1,0；Nickel cobalt manganese persursor material
In sodium impurity content be 0.006%, sulfate radical content is 0.12%, and nickel cobalt manganese persursor material has high crystalline, XRD tables
It is 1256 to levy the middle intensity of characteristic peak 001.
The preparation method of the spherical nickel cobalt manganese persursor material of the present embodiment, comprises the following steps：
(1) prepared after first dissolving nickel sulfate, manganese sulfate and cobaltous sulfate with water respectively and form mixing salt solution, salt-mixture is molten
The total concentration control of three kinds of elements of nickel cobalt manganese is in 115g/L in liquid, and wherein nickel, cobalt, the mol ratio of manganese Metal ion are 5: 2: 3；So
Afterwards by nickel cobalt manganese salt solution be well mixed with reducing agent hydrazine hydrate mixed liquor A (hydrazine hydrate addition be mixing salt solution volume
Fraction 0.05%)；Again by 80g/L sodium hydroxide solution and reducing agent it is well mixed mixed liquid B (hydrazine hydrate addition is
Sodium hydroxide solution volume fraction 0.04%)；20g/L ammoniacal liquor and reducing agent hydrazine hydrate are well mixed to obtain mixed liquor C (water
Close hydrazine addition for sodium hydroxide solution volume fraction 0.04%)；
(2) prepare before reacting：Pure water is added in precipitation reaction kettle, thorough seal processing is carried out to precipitation reaction kettle,
The measure of thorough seal processing includes：Water seal is carried out while carrying out mechanical seal to the agitating shaft of precipitation reaction kettle；To precipitation
It is connected and sealed between the cell body and groove lid of reactor by seal washer；The discharge pipe of precipitation reaction kettle is embedded to water
In；Then pass to nitrogen, then add sodium hydroxide solution and adjust pH value to 10.5, at the same add ammoniacal liquor adjust ammonia ion concentration to
15g/L, while the reducing agent for adding 0.05% obtains reacting bottom liquid, the initial temperature of control reaction bottom liquid is at 50 ± 1 DEG C, it is ensured that
Nitrogen blanket is formed in reactor；
(3) it is co-precipitated：By the mixed liquor A of above-mentioned preparation, mixed liquid B and mixed liquor C, cocurrent is added by measuring pump together
Into the above-mentioned precipitation reaction kettle for handling (seal is good) equipped with reaction bottom liquid and through thorough seal, continous way is proceeded by
Constantly nitrogen is passed through in coprecipitation reaction, course of reaction to be protected, and ties up inert atmosphere in the inner chamber of precipitation reaction kettle
Certain normal pressure is held, to ensure that precipitation environment is in complete anaerobic state；PH value in course of reaction is controlled 10.6~11.1,
The rotating speed of reactor is controlled in 220r/min, and the temperature control of reaction system is at 50 ± 1 DEG C, the concentration control of ammonia in reaction system
For 15g/L, the overall control of solid matter is 150g/L~250g/L, continuous-stable reaction 20h~24h in reaction system, directly
It is complete to the stable reaction of raw material；
(4) ripening：Ageing reaction, ageing are carried out to the slurry continuously overflowed from precipitation reaction kettle after stable reaction
It is that ageing reaction is carried out to slurry using 15wt% alkali lye (sodium hydroxide solution or potassium hydroxide solution) in process step, it is old
It is 60 DEG C to change reaction temperature, and the ageing reaction time is 45min~60min, is in normal temperature by being aged reacted reaction mass
Under be pumped directly into deionized water and washed without separation of solid and liquid, and it is after 8.0, to be washed in pure water dry to wash to pH value
Dried up, dried after net, drying temperature is 125 DEG C, the impurity content for obtaining anode material for lithium-ion batteries after drying is low,
The high spherical nickel cobalt manganese persursor material A of crystallinity.
Comparative example 2：
Reactor does not do thorough seal processing in the present embodiment, remaining condition be the same as Example 1, is settled out yellowish-brown slurry,
Nickel cobalt manganese persursor material B is made.
Comparative example 3：
Reducing agent is not added with each material solution in the present embodiment, remaining condition be the same as Example 1 is settled out yellowish-brown colorant
Slurry, is made nickel cobalt manganese persursor material C.
Comparative example 4：
Slurry first filters drying and is aged again in the present embodiment, and remaining condition be the same as Example 1 is settled out greyish white slurry, is made
Nickel cobalt manganese persursor material D.
To nickel cobalt manganese persursor material A, B, C and D that above prepared by four examples, detected, concrete outcome see the table below
1：
Table 1：The performance test of nickel cobalt manganese persursor material
By carrying out anti-oxidation place to solution deoxygenation, coprecipitation process and ageing process it can be seen from the data of upper table 1
Reason, produces obtained presoma good crystallinity, and impurity content is low.
Claims (4)
1. a kind of preparation method of spherical nickel cobalt manganese persursor material, the chemical molecular formula of the nickel cobalt manganese persursor material is
Ni1-x-yCoxMny(OH)2, wherein the ＜ y ＜ 1 of 0 ＜ x ＜ 1,0；The quality of sodium impurity content in the nickel cobalt manganese persursor material
Fraction≤0.012%, mass fraction≤0.30% of sulfate radical foreign matter content, the nickel cobalt manganese persursor material has highly crystalline
Property, its intensity >=1100 of characteristic peak 001 in XRD spectrum sign, the preparation method includes raw material preparation process, co-precipitation step
Rapid and ripening step, it is characterised in that：Used in the raw material preparation process, co-precipitation step and ripening step
Anti-oxidation measure；
Anti-oxidation measure in the raw material preparation process includes：Various raw materials, the reagent difference that subsequent step is needed to use
Purchased in material solution form, form plurality of raw materials solution, and add in plurality of raw materials solution reducing agent, the reducing agent is
One or more of mixtures in hydrazine hydrate, sodium sulfite, nitrite, and in each material solution reducing agent addition
Measure as the 0.01%~1% of material solution volume fraction；
Anti-oxidation measure in the co-precipitation step includes following multinomial measure：
（1）Thorough seal processing is carried out to precipitation reaction kettle；The measure of the thorough seal processing includes：To precipitation reaction kettle
Agitating shaft carries out carrying out water seal while mechanical seal；To being carried out between the cell body and groove lid of precipitation reaction kettle by seal washer
It is tightly connected；Water seal will be carried out in the discharge pipe insertion water of precipitation reaction kettle；
（2）Before coprecipitation reaction and inert gas is continually fed into course of reaction to be protected, and in the inner chamber of precipitation reaction kettle
In inert atmosphere is maintained certain normal pressure；
Anti-oxidation measure in the ripening step includes：It is old that slurry after coprecipitation reaction is pumped into washing press progress
Change after reaction, be pumped directly into pure water after washes clean and dry up without separation of solid and liquid.
2. preparation method according to claim 1, it is characterised in that the plurality of raw materials solution include precipitant solution,
Enveloping agent solution and the mixing salt solution formed is prepared by nickel salt, cobalt salt, manganese salt, the mixing salt solution is standby according to drawing up
Nickel, cobalt, the mol ratio of three kinds of elements of manganese are prepared in nickle cobalt lithium manganate.
3. preparation method according to claim 2, it is characterised in that the nickel salt, cobalt salt, manganese salt are sulfate, and
The total concentration of three kinds of elements of nickel cobalt manganese is controlled in 60~120 g/L in mixing salt solution；The precipitant solution is sodium hydroxide
The aqueous solution, its concentration control is 80~200 g/L；The enveloping agent solution is ammoniacal liquor, and the control of its concentration is 5~100 g/L.
4. preparation method according to claim 1, it is characterised in that be in the ripening step using 5wt%~
20wt% alkali lye to slurry carry out ageing reaction, ageing reaction temperature be 40 DEG C~80 DEG C, the ageing reaction time for 30min~
60min；It is to be washed at normal temperatures using deionized water by being aged reacted reaction mass, and washing to pH value is
After 7.5~8.5, dried up, dried after washing.
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| CN106328922A (en) * | 2015-06-29 | 2017-01-11 | 河南科隆新能源有限公司 | Modified NCM precursor material and preparation method therefor |
| CN104953112B (en) * | 2015-07-17 | 2017-06-27 | 诸暨帕瓦新能源有限公司 | The preparation method of the coated porous ball-shaped lithium-ion battery material precursors of AlF3 |
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