CN110061208A - Lithium battery anode active material presoma and preparation method thereof, lithium battery anode active material and preparation method thereof and lithium battery - Google Patents
Lithium battery anode active material presoma and preparation method thereof, lithium battery anode active material and preparation method thereof and lithium battery Download PDFInfo
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- CN110061208A CN110061208A CN201910265226.7A CN201910265226A CN110061208A CN 110061208 A CN110061208 A CN 110061208A CN 201910265226 A CN201910265226 A CN 201910265226A CN 110061208 A CN110061208 A CN 110061208A
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/362—Composites
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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 present invention discloses lithium battery anode active material presoma and preparation method thereof, lithium battery anode active material and preparation method thereof and lithium battery.Wherein, the method for preparing lithium battery anode active material presoma includes: that nickel cobalt salting liquid, aluminum salt solution, precipitating reagent and complexing agent is added into reaction bottom liquid to carry out synthetic reaction, obtains mixed slurry；During synthetic reaction carries out, sample is obtained from mixed slurry；The free nickel concentration and the concentration of free ammonia in sample are detected, when free nickel concentration and the concentration of free ammonia reach preset range, mixed slurry is separated by solid-liquid separation, solid product is obtained；Solid product is post-processed, lithium battery anode active material presoma is obtained.The method for preparing lithium battery anode active material passes through the concentration for detecting and controlling dissociate in reaction mixed slurry nickel and free ammonia, and the lithium battery anode active material presoma of high-quality can be prepared.
Description
Technical field
The present invention relates to field of lithium, specifically, the present invention relates to lithium battery anode active material presoma and its
Preparation method, lithium battery anode active material and preparation method thereof and lithium battery.
Background technique
Lithium ion battery is high with its energy density, have a safety feature, have extended cycle life and the advantages such as self discharge is low by
The extensive concern of people.From nineteen ninety after Japan SONY energy technology company makes lithium ion secondary battery viable commercial product,
It is widely used in many portable electronic instrument equipment such as mobile phone, laptop and instrument and meter, meanwhile, electronic
The fields such as automobile, electric tool and energy storage peak shaving power station also have a good application prospect.
Current commercialized anode material for lithium-ion batteries mainly has cobalt acid lithium, spinel lithium manganate, LiFePO4 etc., by
Find various problem in use in it, thus recent years research and development ternary material become a big emphasis, lithium from
Nickel-cobalt-manganese ternary lithium ion anode material development in sub- positive electrode is very swift and violent, exactly the synergistic effect of nickel cobalt manganese, nickel cobalt
Manganese ternary anode material for lithium-ion batteries combines LiNiO2、LiCoO2、LiMn2O4The advantages of three kinds of layer structure materials, have
Height ratio capacity, the features such as cost is relatively low, stable cycle performance, preferable security performance, it is considered to be preferably substitution LiCoO2Just
Pole material.And there are high production cost, particle size for lithium ion secondary battery nickel-cobalt-manganternary ternary anode material in current technology
Greatly, size distribution is wide and particle agglomeration phenomenon and the defects of irreversible capacity is larger for the first time.
The quality of tertiary cathode material performance depends primarily on the quality of ternary anode material precursor.Currently, domestic factory
Family production ternary anode material precursor impurity content it is generally higher, especially influence battery safety Fe, Cr, Cu and
The impurity contents such as Zn are higher, these foreign metals can dissolve out in battery charge and discharge process, move to cathode and formation branch is precipitated
Crystalline substance, these foreign metal dendrite can pierce through diaphragm and cause battery micro-short circuit, and battery core temperature is caused to increase, and deteriorate battery electrochemical
Can, or even battery thermal runaway is caused, eventually lead to cells burst explosion.However, existing prepare lithium battery anode active material
The method of presoma still has much room for improvement.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose lithium battery anode active material presoma and preparation method thereof, lithium battery anode active material and its system
Preparation Method and lithium battery.Wherein, the method for lithium battery anode active material is prepared by detecting and controlling in reaction mixed slurry
The concentration of free nickel and free ammonia, can be prepared the lithium battery anode active material presoma of high-quality.
In one aspect of the invention, the invention proposes a kind of sides for preparing lithium battery anode active material presoma
Method.According to an embodiment of the invention, this method comprises: nickel cobalt salting liquid, aluminum salt solution, precipitating is added into reaction bottom liquid in (1)
Agent and complexing agent carry out synthetic reaction, obtain mixed slurry；During the synthetic reaction carries out, from the mixed slurry
Middle acquisition sample；(2) the free nickel concentration and the concentration of free ammonia in the sample are detected, when the free nickel concentration and the trip
When reaching preset range from ammonia density, the mixed slurry is separated by solid-liquid separation, solid product is obtained；(3) to the solid phase
Product is post-processed, and the lithium battery anode active material presoma is obtained.
The method according to an embodiment of the present invention for preparing lithium battery anode active material presoma, by molten from nickel cobalt salt
Liquid, aluminium salt, precipitating reagent and complexing agent mixed slurry in sample detection, can be according to dissociating nickel in reaction paste and free ammonia contain
The parameters such as granularity, the tap density for measuring to judge positive electrode active materials presoma product indirectly.Inventors have found that in presoma
In synthetic reaction, the flow of complexing agent and precipitating reagent, adjustable reaction mixed slurry are supplied into reaction system by adjusting
In dissociate the content of nickel and free ammonia, and then can control the particle size growth of positive electrode active materials presoma.It is living in anode as a result,
Property material precursor synthetic reaction in, by control complexing agent and precipitating reagent flow so that in mixed slurry sample dissociate nickel
Concentration and the concentration of free ammonia reach preset range, can be obtained the positive electrode active materials of high-quality.
In addition, the method according to the above embodiment of the present invention for preparing lithium battery anode active material presoma can also have
There is following additional technical characteristic:
In some embodiments of the invention, in the nickel cobalt salting liquid, Ni2+Concentration is 1.6~2.0mol/L, Co2+It is dense
Degree is 0.3~0.375mol/L.
In some embodiments of the invention, AlO in the aluminum salt solution2 -Concentration is 0.3~0.625mol/L.
In some embodiments of the invention, the bottom liquid that reacts is the mixed liquor of ammonium hydroxide and water, in the liquid of the reaction bottom,
The volumetric concentration of the ammonium hydroxide is 1.0%~3.0%, NH in the ammonium hydroxide3Mass concentration be 25%~28%.
In some embodiments of the invention, the pH value of the reaction bottom liquid is 11~12.
In some embodiments of the invention, the temperature of the reaction bottom liquid is 50~60 DEG C.
In some embodiments of the invention, the precipitating reagent is that the sodium hydroxide that mass concentration is 25%~40% is water-soluble
Liquid.
In some embodiments of the invention, the complexing agent is the ammonium hydroxide that mass concentration is 15%~25%.
In some embodiments of the invention, the preset range of the free nickel concentration is 0~0.1mol/L, described free
The preset range of ammonia density is 11.0~11.5g/L.
In some embodiments of the invention, the nickel cobalt salting liquid, the aluminium salt is being added into reaction bottom liquid
During solution, the precipitating reagent and the complexing agent, the flow velocity of the nickel cobalt salting liquid is 50~60mL/min, the aluminium
The flow velocity of salting liquid is 5~15mL/min, and the flow velocity of the precipitating reagent is 10~12mL/min, and the flow velocity of the complexing agent is 4
~5 mL/min.
In some embodiments of the invention, in step (2), by the sample stratification, the sample is then detected
Free nickel content and free ammonia content in supernatant.
In some embodiments of the invention, the post-processing includes: that alkali bubble, washing are successively carried out to the solid product
And drying.
In another aspect of this invention, the invention proposes a kind of lithium battery anode active material presomas.According to this hair
Bright embodiment, the lithium battery anode active material presoma be by above-described embodiment prepare lithium battery anode active material before
What the method for driving body was prepared.The impurity content of the lithium battery anode active material presoma is low as a result, granularity is suitable for, vibration
Real density is high, and comprehensive performance is outstanding.
In another aspect of the invention, the invention proposes a kind of methods of lithium battery anode active material.According to this hair
Bright embodiment, this method comprises: the method system for preparing lithium battery anode active material presoma of (a) according to above-described embodiment
It is standby to obtain positive electrode active materials presoma；(b) the positive electrode active materials presoma is mixed and is roasted with lithium source, obtained
The lithium battery anode active material.The impurity content for the lithium battery anode active material being prepared as a result, by this method
Low, granularity is suitable for, tap density is high, and comprehensive performance is outstanding.
In still another aspect of the invention, the invention proposes a kind of lithium battery anode active materials.Reality according to the present invention
Example is applied, which be prepared by the method for preparing lithium battery anode active material of above-described embodiment
's.The impurity content of the lithium battery anode active material is low as a result, granularity is suitable for, tap density is high, and comprehensive performance is outstanding.
In still another aspect of the invention, the invention proposes a kind of lithium batteries.According to an embodiment of the invention, the lithium battery
It include: anode pole piece, diaphragm, cathode pole piece and electrolyte；Wherein, the anode pole piece includes plus plate current-collecting body and is formed in institute
The positive electrode on plus plate current-collecting body surface is stated, the positive electrode includes the lithium battery anode active material of above-described embodiment.It should
Lithium battery has outstanding cyclical stability and reliability by using the positive electrode active materials of above-described embodiment.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the method flow signal according to an embodiment of the invention for preparing lithium battery anode active material presoma
Figure.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In one aspect of the invention, the invention proposes a kind of sides for preparing lithium battery anode active material presoma
Method.According to an embodiment of the invention, this method comprises: nickel cobalt salting liquid, aluminum salt solution, precipitating is added into reaction bottom liquid in (1)
Agent and complexing agent carry out synthetic reaction, obtain mixed slurry；During synthetic reaction carries out, examination is obtained from mixed slurry
Sample；(2) the free nickel concentration and the concentration of free ammonia in sample are detected, when free nickel concentration and the concentration of free ammonia reach preset range
When, mixed slurry is separated by solid-liquid separation, solid product is obtained；(3) solid product is post-processed, obtains lithium battery anode
Active material presoma.
The method according to an embodiment of the present invention for preparing lithium battery anode active material presoma, by molten from nickel cobalt salt
Liquid, aluminum salt solution, precipitating reagent and complexing agent mixed slurry in sample detection, can be according to the nickel and free of dissociating in reaction paste
Ammonia content is come parameters such as the granularity, the tap densities that judge positive electrode active materials presoma product indirectly.Inventors have found that preceding
It drives in body synthetic reaction, supplies the flow of complexing agent and precipitating reagent, adjustable reaction mixing into reaction system by adjusting
The content of free nickel and free ammonia in slurry, and then can control the particle size growth of positive electrode active materials presoma.As a result, just
In the synthetic reaction of pole active material presoma, by the flow of control complexing agent and precipitating reagent so that mixed slurry sample middle reaches
Reach preset range from nickel concentration and the concentration of free ammonia, can be obtained the positive electrode active materials of high-quality.
Below with reference to Fig. 1 further to the side according to an embodiment of the present invention for preparing lithium battery anode active material presoma
Method is described in detail.According to an embodiment of the invention, this method comprises:
S100: synthetic reaction, sampling
In the step, nickel cobalt salting liquid, aluminum salt solution, precipitating reagent and complexing agent are added into reaction bottom liquid and synthesize instead
It answers, obtains mixed slurry；During synthetic reaction carries out, sample is obtained from mixed slurry.It is according to the present invention specific
Example, synthetic reaction can be carried out with the common synthesis reaction vessel in this field, reaction bottom liquid are added in reaction kettle in advance, then leads to
It crosses different feed inlets and supplies nickel cobalt salting liquid, aluminum salt solution, precipitating reagent and complexing agent into reaction kettle respectively, synthesize anti-
It answers.
According to some embodiments of the present invention, above-mentioned nickel cobalt salting liquid can by common nickel salt, cobalt salt and water (preferably go from
Sub- water) it is mixed with to obtain.Specific example according to the present invention, nickel salt can be in nickel sulfate, nickel nitrate, nickel chlorides
At least one；Cobalt salt can be for selected from least one of cobaltous sulfate, cobalt nitrate, cobalt chloride.In above-mentioned nickel cobalt salting liquid,
Ni2+Concentration is 1.6~2.0mol/L, Co2+Concentration is 0.3~0.375mol/L.Ni in nickel cobalt salt as a result,2+、Co2+Concentration is suitable
Preferably, it is easy to adjust its concentration in a kettle by adjusting its flow, thus before obtaining the positive electrode active materials of high-quality
Drive body.
According to some embodiments of the present invention, AlO in aluminum salt solution2 -Concentration is 0.3~0.625mol/L.According to the present invention
Some embodiments, aluminum salt solution employed in the method for the present invention can prepare in accordance with the following methods: by common aluminium salt (such as
Aluminum sulfate, aluminium chloride, aluminum nitrate etc.) it is mixed with appropriate sodium hydroxide and water to meet above-mentioned concentration requirement, it is then mixed to gained
It closes liquid to be filtered, removes flocculent deposit, obtain aluminum salt solution.In addition, solution hair should be avoided in aluminum salt solution process for preparation
It is yellow.
According to some embodiments of the present invention, above-mentioned reaction bottom liquid is the mixed liquor of ammonium hydroxide and water, in reaction bottom liquid, ammonia
The volumetric concentration of water is 1.0%~3.0%, NH in ammonium hydroxide3Mass concentration be 25%~28%.As a result, at above-mentioned reaction bottom
In liquid, the impurity content that nickel cobalt salt reacts generation positive electrode active materials presoma with aluminium salt is lower, the performances such as granularity, tap density
More preferably.
According to some embodiments of the present invention, the pH value of above-mentioned reaction bottom liquid is 11~12, it is preferred that the pH of reaction bottom liquid
Value is 11.30~11.50, specifically, can adjust using sodium hydroxide the pH of reaction bottom liquid in the reaction bottom liquid preparation stage
It is worth to above range.As a result, in the liquid of above-mentioned reaction bottom, nickel cobalt salt is reacted with aluminium salt generates the miscellaneous of positive electrode active materials presoma
Matter content is lower, and the performances such as granularity, tap density are more preferably.
According to some embodiments of the present invention, the temperature of above-mentioned reaction bottom liquid is 55~70 DEG C, it is preferred that reaction bottom liquid
Temperature is 60 DEG C.As a result, in the liquid of above-mentioned reaction bottom, nickel cobalt salt reacts the impurity for generating positive electrode active materials presoma with aluminium salt
Content is lower, and the performances such as granularity, tap density are more preferably.
According to some embodiments of the present invention, above-mentioned precipitating reagent is that the sodium hydroxide that mass concentration is 25%~40% is water-soluble
Liquid.Precipitating reagent will not introduce the foreign ion for being difficult to remove into reaction system as a result, and concentration is suitable for, it is easy to synthesize
The parameters such as pH value of reaction system, extent of reaction are adjusted in reaction by the flow velocity of condition precipitating reagent, to further decrease production
The impurity content of product further improves the performances such as granularity, the tap density of product.
According to some embodiments of the present invention, above-mentioned complexing agent is the ammonium hydroxide that mass concentration is 15%~25%.Network as a result,
Mixture will not introduce the foreign ion for being difficult to remove into reaction system, and concentration is suitable for, it is easy to pass through in synthetic reaction
The flow velocity of condition complexing agent adjusts the parameters such as pH value of reaction system, extent of reaction, so that the impurity for further decreasing product contains
Amount further improves the performances such as granularity, the tap density of product.
Further, according to some embodiments of the present invention, after reacting bottom hydroful foot condition as previously described, Xiang Fanying
Nickel cobalt salting liquid, aluminum salt solution, precipitating reagent and complexing agent is added in the liquid of bottom simultaneously, starts synthetic reaction.According to the present invention one
A little embodiments, synthetic reaction carry out under the speed of agitator of 600~1200rpm (preferably 800rpm), to be further ensured that each original
Material is sufficiently mixed uniformly.In addition, high-purity raw should be used in synthetic reaction, avoid leading to product impurity content because of material purity
It is excessively high.
S200: detection sample, separation solid product
In the step, the free nickel concentration and the concentration of free ammonia in sample are detected, when free nickel concentration and the concentration of free ammonia
When reaching preset range, mixed slurry is separated by solid-liquid separation, obtains solid product.Inventors have found that dissociating in reaction system
The concentration of nickel and free ammonia can change with the variation of extent of reaction, and the concentration of free nickel and free ammonia can in reaction system
To characterize the performance parameters such as impurity content, granularity, the tap density of the positive electrode active materials presoma that are prepared.It that is to say
It says, by the concentration of dissociate in control reaction system nickel and free ammonia, can control the positive electrode active materials forerunner being prepared
The performance parameters such as impurity content, granularity, the tap density of body, when free nickel concentration and the concentration of free ammonia reach preset range,
Indicate that properties of product have reached requirement.In turn, inventor inputs nickel cobalt into reaction bottom liquid by further investigation, discovery control
Salting liquid, aluminum salt solution, precipitating reagent and complexing agent flow velocity, can control in reaction system dissociate nickel and free ammonia concentration.
The method for preparing positive electrode active materials presoma of the invention as a result, by control to reaction bottom liquid in input nickel cobalt salting liquid,
The flow velocity of aluminum salt solution, precipitating reagent and complexing agent come adjust in reaction system dissociate nickel and free ammonia concentration, height can be obtained
The positive electrode active materials presoma product of quality.Further, when nickel concentration free in reaction system and the concentration of free ammonia reach
When preset range, mixed slurry is separated by solid-liquid separation, to separate positive electrode active materials presoma from reaction system.
According to some embodiments of the present invention, dissociate nickel concentration preset range be 0~0.1g/L, the concentration of free ammonia it is pre-
Determining range is 11.0~11.5g/L, and the pH value of reaction system is about 11.60~11.80 at this time.When in reaction system dissociate nickel with
When the concentration of free ammonia reaches above range, the granularity that positive electrode active materials presoma product is prepared can achieve D50=8~
10 μm, tap density be not less than 1.8g/cm3Design standard, and impurity content is extremely low, and product comprehensive performance is outstanding.
According to some embodiments of the present invention, to reaction bottom liquid in be added nickel cobalt salting liquid, aluminum salt solution, precipitating reagent and
During complexing agent, the flow velocity of nickel cobalt salting liquid is 50~60mL/min, and the flow velocity of aluminum salt solution is 5~15mL/min, is sunk
The flow velocity of shallow lake agent is 10~12mL/min, and the flow velocity of complexing agent is 4~5mL/min.By controlling the flow velocity of each raw material above-mentioned
Range, it is easy to which the free nickel and the concentration of free ammonia controlled in reaction system reaches preset range, so that high-quality be prepared
Positive electrode active materials presoma product.Specific example according to the present invention, above-mentioned each raw material can pass through peristaltic pump and electromagnetism
Metering pump is input in reaction system.
According to some embodiments of the present invention, in S200, by sample stratification, the trip in sample supernatant is then detected
From nickel concentration and the concentration of free ammonia.Inventors have found that in synthetic reaction, reaction system is in suspended liquid status, by will be from anti-
The sample stratification taken out in system is answered to obtain supernatant, when standing, needs to seal the spilling to prevent NH3, then examine
The free nickel concentration and the concentration of free ammonia in supernatant are surveyed, is operated more easy.In addition, it is necessary to explanation, sample, which is stood, to be divided
Free nickel concentration and the concentration of free ammonia are consistent with nickel concentration free in reaction system and the concentration of free ammonia in layer gained supernatant.
S300: post-processing
In the step, solid product is post-processed, obtains lithium battery anode active material presoma.As previously mentioned,
Contain the positive electrode active materials presoma for reaching design standard in the solid product.By being post-processed to the solid product,
To obtain lithium battery anode active material presoma product.
According to some embodiments of the present invention, above-mentioned post-processing includes: successively to carry out alkali bubble, washing and baking to solid product
It is dry.Specifically, can steep and be washed until aqueous pH values are 8~9 to solid product alkali base, then separation of solid and liquid is precipitated
Object.Again by the sediment 80~120 DEG C dry 20~for 24 hours, obtain lithium battery anode active material presoma product.
In another aspect of this invention, the invention proposes a kind of lithium battery anode active material presomas.According to this hair
Bright embodiment, the lithium battery anode active material presoma be by above-described embodiment prepare lithium battery anode active material before
What the method for driving body was prepared.The impurity content of the lithium battery anode active material presoma is low as a result, granularity is suitable for, vibration
Real density is high, and comprehensive performance is outstanding.In addition, it is necessary to explanation, described previously for " preparing lithium battery anode active material presoma
Method " whole feature and advantage of the description are equally applicable to the lithium battery anode active material presoma, herein no longer
It repeats one by one.
In another aspect of the invention, the invention proposes a kind of methods of lithium battery anode active material.According to this hair
Bright embodiment, this method comprises: the method system for preparing lithium battery anode active material presoma of (a) according to above-described embodiment
It is standby to obtain positive electrode active materials presoma；(b) positive electrode active materials presoma is mixed and is roasted with lithium source, obtain lithium electricity
Pond positive electrode active materials.The impurity content for the lithium battery anode active material being prepared as a result, by this method is low, granularity is suitable
Preferably, tap density is high, and comprehensive performance is outstanding.
It should be noted that step (b), can adopt positive electrode active materials presoma and lithium with the conventional methods in the field
Source mixes and is roasted, for example, specific example according to the present invention, lithium source can choose the inorganic salts of lithium, such as lithium nitrate, carbon
Sour lithium, a hydronium(ion) lithia etc..The mixed proportion of positive electrode active materials presoma and lithium source is also not particularly limited, Ke Yigen
It is determined according to the chemical composition of oxidate for lithium；Calcination process can carry out under 600~800 DEG C of maturing temperature.In addition, it is necessary to say
Bright, which has described previously for " preparing lithium battery anode active material forerunner
Whole feature and advantage described in the method for body ", this is no longer going to repeat them.
In still another aspect of the invention, the invention proposes a kind of lithium battery anode active materials.Reality according to the present invention
Example is applied, which be prepared by the method for preparing lithium battery anode active material of above-described embodiment
's.The impurity content of the lithium battery anode active material is low as a result, granularity is suitable for, tap density is high, and comprehensive performance is outstanding.Separately
Outside, it should be noted that whole features described previously for " method for preparing lithium battery anode active material " described description and excellent
Point is equally applicable to the lithium battery anode active material, and this is no longer going to repeat them.
In still another aspect of the invention, the invention proposes a kind of lithium batteries.According to an embodiment of the invention, the lithium battery
It include: anode pole piece, diaphragm, cathode pole piece and electrolyte；Wherein, the anode pole piece includes plus plate current-collecting body and is formed in institute
The positive electrode on plus plate current-collecting body surface is stated, the positive electrode includes the lithium battery anode active material of above-described embodiment.It should
Lithium battery has outstanding cyclical stability and reliability by using the positive electrode active materials of above-described embodiment.In addition, it is necessary to
Illustrate, which has described previously for whole feature and advantage described in " lithium battery anode active material ", herein
No longer repeat one by one.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
(1) raw material preparation
Reaction bottom liquid: ammonium hydroxide is mixed with deionized water according to the volumetric concentration of ammonium hydroxide for 1.0%, NH in ammonium hydroxide3Matter
Measuring concentration is 25%；
Nickel cobalt salting liquid: nickel sulfate, cobaltous sulfate are added in appropriate amount of deionized water according to molar ratio 0.8:0.15, stirring
After uniformly, in gained nickel cobalt salting liquid, Ni2+Concentration is 1.6mol/L, Co2+Concentration is 0.3mol/L；
Aluminum salt solution: aluminum sulfate, sodium hydroxide are added in appropriate amount of deionized water according to mass ratio 0.125:0.252,
After mixing evenly, it is filtered to remove flocculent deposit, in gained aluminum salt solution, AlO2 -Concentration is 0.5mol/L；
Precipitating reagent: the sodium hydrate aqueous solution that mass concentration is 25%；
Complexing agent: the ammonium hydroxide that mass concentration is 15%.
(2) synthetic reaction
Deionized water is added into 20L synthesis reaction vessel, until stopping being added when deionized water will overflow reaction kettle going
Ionized water, and deionized water is warming up to 60 DEG C, ammonium hydroxide is added under 800rpm revolving speed, obtains reaction bottom liquid, utilizes hydroxide
It is 11.8~12.0g/L, pH value to 11.80~12.00 that sodium solution, which adjusts reaction bottom liquid to free ammonia,；Using peristaltic pump to reaction
Nickel cobalt salting liquid, aluminum salt solution, precipitating reagent and complexing agent is added in the liquid of bottom simultaneously respectively, the pH value of maintenance reaction bottom liquid is
11.60~11.80；Wherein, nickel cobalt salting liquid flow velocity is 50mL/min, and aluminum salt solution flow velocity is 10mL/min, precipitating reagent flow velocity
For 10mL/min, complexing agent flow velocity is 4mL/min.
(3) sample detection
After synthetic reaction carries out stationary phase, 20mL slurry is sampled from reaction paste, stratification passes through acid-base titration
Detecting the free nickel content in sample supernatant is 0~0.1g/L, and the concentration of free ammonia is 11.0~11.5g/L, is had reached predetermined
Concentration range.
(4) it is separated by solid-liquid separation
Reaction kettle is discharged in reaction paste (suspension), slurry is separated by solid-liquid separation, collects solid product.
(5) it post-processes
Alkali bubble and washing are carried out to solid product obtained by step (4), until aqueous pH values are 8, are separated by solid-liquid separation and collect precipitating
Object；Sediment is dried for 24 hours at 100 DEG C, obtains NCA ternary material precursor, granularity D50=9.0 ± 1 μm, tap density
For 1.80g/cm3。
Embodiment 2
(1) raw material preparation
Reaction bottom liquid: ammonium hydroxide is mixed with deionized water according to the volumetric concentration of ammonium hydroxide for 2.0%, NH in ammonium hydroxide3Matter
Measuring concentration is 26.5%；
Nickel cobalt salting liquid: nickel sulfate, cobaltous sulfate are added in appropriate amount of deionized water according to molar ratio 0.8:0.15, stirring
After uniformly, in gained nickel cobalt salting liquid, Ni2+Concentration is 2.0mol/L, Co2+Concentration is 0.375mol/L；
Aluminum salt solution: aluminum sulfate, sodium hydroxide are added in appropriate amount of deionized water according to mass ratio 0.125:0.252,
After mixing evenly, it is filtered to remove flocculent deposit, in gained aluminum salt solution, AlO2 -Concentration is 0.625mol/L；
Precipitating reagent: the sodium hydrate aqueous solution that mass concentration is 32%；
Complexing agent: the ammonium hydroxide that mass concentration is 18%.
(2) synthetic reaction
Deionized water is added into 20L synthesis reaction vessel, until stopping being added when deionized water will overflow reaction kettle going
Ionized water, and deionized water is warming up to 60 DEG C, ammonium hydroxide is added under 800rpm revolving speed, obtains reaction bottom liquid, utilizes hydroxide
It is 11.8~12.0g/L, pH value to 11.80~12.00 that sodium solution, which adjusts reaction bottom liquid to free ammonia,；Using electromagnetic dosing pump to
Nickel cobalt salting liquid, aluminum salt solution, precipitating reagent and complexing agent is added in reaction bottom liquid simultaneously respectively, the pH value of maintenance reaction bottom liquid is
11.60~11.80；Wherein, nickel cobalt salting liquid flow velocity is 50mL/min, and aluminum salt solution flow velocity is 10mL/min, precipitating reagent flow velocity
For 10mL/min, complexing agent flow velocity is 6mL/min.
(3) sample detection
After synthetic reaction carries out stationary phase, 20mL slurry is sampled from reaction paste, stratification passes through autotitrator
Using acid-base titration detection sample supernatant in free nickel content be 0~0.1g/L, the concentration of free ammonia be 11.0~
11.5g/L has reached predetermined concentration range.
(4) it is separated by solid-liquid separation
Reaction kettle is discharged in reaction paste (suspension), slurry is separated by solid-liquid separation, collects solid product.
(5) it post-processes
Alkali bubble and washing are carried out to solid product obtained by step (4), until aqueous pH values are 8.5, separation of solid and liquid is collected heavy
Starch；Sediment is dried into 20h at 120 DEG C, obtains NCM ternary material precursor, granularity D50=9.0 ± 1 μm, vibration density
Degree is 1.82g/cm3。
Embodiment 3
Presoma and lithium carbonate according to mass ratio are 1 by the NCA ternary material precursor that Example 1 is prepared:
1.05 mixing, and 15h is roasted at 700 DEG C of pre-burning 5h, 780 DEG C, obtain NCA ternary material.
Embodiment 4
The NCA ternary material precursor that Example 2 is prepared, by presoma and a hydronium(ion) lithia according to quality
Than for 1:1.06 mixing, and 20h is roasted at 500 DEG C of pre-burning 5h, 760 DEG C, obtains NCA ternary material.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of method for preparing lithium battery anode active material presoma characterized by comprising
(1) nickel cobalt salting liquid, aluminum salt solution, precipitating reagent and complexing agent is added into reaction bottom liquid and carries out synthetic reaction, mixed
Close slurry；During the synthetic reaction carries out, sample is obtained from the mixed slurry；
(2) the free nickel concentration and the concentration of free ammonia in the sample are detected, when the free nickel concentration and the free ammonia are dense
When degree reaches preset range, the mixed slurry is separated by solid-liquid separation, solid product is obtained；
(3) solid product is post-processed, obtains the lithium battery anode active material presoma.
2. the method according to claim 1, wherein in the nickel cobalt salting liquid, Ni2+Concentration be 1.6~
2.0mol/L, Co2+Concentration is 0.3~0.375mol/L；
Optionally, AlO in the aluminum salt solution2 -Concentration is 0.3~0.625mol/L；
Optionally, the bottom liquid that reacts is the mixed liquor of ammonium hydroxide and water, and in the liquid of the reaction bottom, the volumetric concentration of the ammonium hydroxide is
1.0%~3.0%, NH in the ammonium hydroxide3Mass concentration be 25%~28%；
Optionally, the pH value of the reaction bottom liquid is 11~12；
Optionally, the temperature of the reaction bottom liquid is 50~60 DEG C；
Optionally, the precipitating reagent is the sodium hydrate aqueous solution that mass concentration is 25%~40%；
Optionally, the complexing agent is the ammonium hydroxide that mass concentration is 15%~25%.
3. the method according to claim 1, wherein the preset range of the free nickel concentration be 0~0.1g/L,
The preset range of described the concentration of free ammonia is 11.0~11.5g/L.
4. the method according to claim 1, wherein molten the nickel cobalt salt is added into reaction bottom liquid
During liquid, the aluminum salt solution, the precipitating reagent and the complexing agent, the flow velocity of the nickel cobalt salting liquid is 50~
60mL/min, the flow velocity of the aluminum salt solution are 5~15mL/min, and the flow velocity of the precipitating reagent is 10~12mL/min, described
The flow velocity of complexing agent is 4~5mL/min.
5. the method according to claim 1, wherein by the sample stratification, then being examined in step (2)
Survey the free nickel concentration and the concentration of free ammonia in the sample supernatant.
6. the method according to claim 1, wherein it is described post-processing include: to the solid product successively into
Row alkali bubble, washing and drying.
7. a kind of lithium battery anode active material presoma, which is characterized in that the lithium battery anode active material presoma is
It is prepared by the described in any item methods of claim 1~6.
8. a kind of method for preparing lithium battery anode active material characterized by comprising
(a) positive electrode active materials presoma is prepared according to the described in any item methods of claim 1~6；
(b) the positive electrode active materials presoma is mixed and is roasted with lithium source, obtain the lithium battery anode activity material
Material.
9. a kind of lithium battery anode active material, which is characterized in that the lithium battery anode active material is by claim 8 institute
What the method stated was prepared.
10. a kind of lithium battery characterized by comprising anode pole piece, diaphragm, cathode pole piece and electrolyte；Wherein, it is described just
Pole pole piece includes plus plate current-collecting body and the positive electrode for being formed in the plus plate current-collecting body surface, and the positive electrode includes right
It is required that lithium battery anode active material described in 9.
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