CN109896552A - A kind of preparation method for mixing aluminium lithium ion anode material presoma - Google Patents
A kind of preparation method for mixing aluminium lithium ion anode material presoma Download PDFInfo
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Abstract
The invention discloses a kind of preparation method for mixing aluminium lithium ion anode material presoma, it is spare to prepare cobalt liquor, liquid alkaline solution, aluminium-complex liquid mixed solution by S1；Reaction kettle is added from reaction kettle side cocurrent in cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution by S2, and reaction kettle is added from the reaction kettle other side with metering method in liquid alkaline solution；S3 is stirred by the solution that auger impeller will be added in reaction kettle, and controls the pH value about 12.4 of solution；S4, the solution stand that will be uniformly mixed in reaction kettle, by supernatant liquid filtering into aging tank；Reactant after ageing is sintered and is mixed and criticized except magnetic treatment, obtained finished product and mix alumina cobalt precursor by S5.Present invention process is simple, and cost is relatively low, is guaranteeing prepared while mixing aluminium lithium ion anode material presoma intensity, it is more uniform that prepared aluminium element is uniformly distributed in presoma, has good practicability.
Description
Technical field
The present invention relates to new energy battery material technical fields more particularly to one kind to mix aluminium lithium ion anode material presoma
Preparation method.
Background technique
Lithium ion battery high-voltage has several developing direction: the mutually homogeneous doping of body, the doping of body phase nonuniformity, core-shell structure；
The wherein mutually homogeneous doping of body, mostly important to the selection of doping phase, in lithium ion battery, generally selection Zr, Al, Ti, Mg makees
To adulterate phase, for improving the crystal structural stability of the anode material for lithium-ion batteries under high charge voltage status.Aluminium is one
The ideal doping phase of kind, can greatly enhance the crystal stability of positive electrode.But to accomplish lithium ion anode material
In material, it is ensured that adulterate an even property for phase, at least same ball layer necessary even one, otherwise, battery can adulterate mutually few ground
Side forms weak spot, in high voltage charge and discharge process, can preferentially form crystal structure collapsing, it is whole to seriously affect lithium ion battery
Body performance.
Aluminium adulterates phase, and performance is good, but introduces sintering as additive in later period positive electrode sintering process, due to aluminium
Stability, seeping at high temperature it is poor, need high temperature that the aluminium high-temp solid of incorporation could be allowed to be diffused into positive electrode, meeting
Greatly improve sintering energy consumption.
NCM ternary precursor is exactly to carry out test or industrial production using preparation fixed proportion blend solution in advance at present,
Since aluminium ion easily hydrolyzes, the aluminium that can be stabilized is can be only present in strongly acidic aqueous solution, by by aluminium and its
Its metal fit together jointly be prepared into required ratio to mix aluminium presoma unreasonable, need using other doped forms.
The mixed method synthetic method used now mixes aluminium in presoma, alumina in Nano level is directly proportionally pumped into anti-
It answers kettle to be prepared and mixes aluminium presoma, the intensity of presoma can be greatly improved in the incorporation of aluminium, but before aluminium still cannot be mixed uniformly
It drives in body, alumina particle can be clearly visible on presoma surface.
Summary of the invention
The purpose of the present invention is to solve disadvantage existing in the prior art, one kind of proposition mixes aluminium lithium ion anode material
The preparation method of material precursor mixes aluminium during the precursor preparation of lithium ion anode material, is guaranteeing do not have to production system
Under the premise of having too great fluctuation process, aluminium is doped in lithium ion anode material in the form of reasonable.
To achieve the goals above, present invention employs following technical solutions:
A kind of preparation method for mixing aluminium lithium ion anode material presoma, includes the following steps:
It is spare to prepare cobalt liquor, liquid alkaline solution, aluminium-complex liquid mixed solution by S1；
Reaction kettle is added from reaction kettle side cocurrent, by liquid alkaline solution in cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution by S2
Reaction kettle is added from the reaction kettle other side with metering method；
S3 is stirred by the solution that auger impeller will be added in reaction kettle, and controls the pH value of solution about
12.4；
S4, the solution stand that will be uniformly mixed in reaction kettle, by supernatant liquid filtering into aging tank；
Reactant after ageing is sintered and is mixed and criticized except magnetic treatment, obtained finished product and mix alumina cobalt precursor by S5.
Preferably, in S1, the aluminium-complex liquid mixed solution be mixed with by compound complex liquid and aluminum solutions and
At compound complex liquid is that 5~10:10~15:10 ratio is mixed with by 20% ammonium hydroxide, 40% ammonium sulfate and pure water by volume
It forms, aluminum solutions are dissolved in mixed acid by aluminium dioxide to be prepared, and mixed acid is 2 by 37% hydrochloric acid and 60% nitric acid by volume
The ratio of~4:0.5~1.5 is mixed to get, and the pH of aluminum solutions is controlled less than 0.5, and following reaction occurs:
The mass concentration of aluminium is 0.015~1.1g/L in aluminium-complex liquid mixed solution.
Preferably, in S1, aluminum solutions is added in compound complex liquid and prepare aluminium-complex liquid mixed solution, aluminium-network
The mass concentration for closing aluminium in liquid mixed solution is 0.015~1.1g/L, and the cobalt source for preparing cobalt liquor is cobalt salt, and cobalt salt uses nitric acid
At least one of cobalt, cobalt chloride and cobaltous sulfate, concentration of cobalt ions is 80-120g/L in cobalt liquor, the hydrogen-oxygen in liquid alkaline solution
Change na concn is 2.5~4mol/L.
Preferably, in S2, by cobalt liquor, ammonium hydroxide and aluminium-complex liquid pass through respectively after constant displacement pump quantitatively conveys by
Parallel pipeline is sent in reaction kettle from the bottom of reaction kettle.
Preferably, in S2, by solubility be 1-5% liquid alkaline solution in such a way that finished product metering pump quantitatively conveys
Out of the top of reaction kettle spray to reaction kettle, controlling the temperature in reaction kettle is 40-80 DEG C.
Preferably, in S2, the flow-rate ratio of cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution and liquid alkaline solution
For 1:(0.1-10), following reaction occurs for whole process:
。
Preferably, in S3, agitator arm is with the stirring rate of 50-200r/min to the reaction solution in reaction kettle
Centrifugal mixer is carried out, while agitating the supplying nitrogen into reaction kettle.
Preferably, in S4, the solution stand 30-90min in reaction kettle carried out supernatant precipitation solution
Filter, leave and take filter D50 be 6-18um reaction solution, the reaction solution filtered out continues to employ as the bottom liquid of reaction kettle secondary response.
Preferably, in S5, sintering process uses three-stage sintering, and first segment sintering temperature is 200~350 DEG C, when
Between be 1-3 hour, second segment sintering temperature be 450~500 DEG C, the time be 2~5 hours, third section burn be sintered junction temperature be
650-750 DEG C, the time is 3~6 hours, and following reaction occurs:
。
Preferably, in S4, time of ageing is 45-90min, in S5, sintering and mixed batch except magnetic treatment when
Between be 6-9h.
Compared with prior art, the invention has the following advantages:
Aluminium lithium ion anode material presoma is mixed using present invention process synthesis, aluminium element is uniformly distributed in presoma, electricity
It shows as being co-precipitated state entirely without the homogeneous of obvious second phase under mirror, hence it is evident that it is better than nano aluminium oxide doping type presoma, and
The anode material of lithium battery performance of even particle size, back segment preparation is more preferable, is conducive to the producing line yield of lithium battery product, controls
Liquid alkaline consumption rationally adjusts the pH value of reaction solution, guarantees the balance entirely reacted, and mixes aluminium lithium ion prepared by guaranteeing
While positive electrode material precursor intensity, it is more uniform that prepared aluminium element is uniformly distributed in presoma, effectively compensates for
The defect of the prior art has good practicability.
Detailed description of the invention
Fig. 1 mixes aluminium lithium ion anode material presoma energy spectrum diagram to be prepared by the present invention.
Fig. 2 mixes aluminium lithium ion anode material presoma electron microscope to be prepared by the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.
Embodiment 1
As shown in attached drawing 1-2, the present embodiment provides a kind of preparation method for mixing aluminium lithium ion anode material presoma, including it is following
Step:
It is spare to prepare cobalt liquor, liquid alkaline solution, aluminium-complex liquid mixed solution by S1；
In S1, the aluminium-complex liquid mixed solution is mixed with by compound complex liquid and aluminum solutions, compound complex liquid by
20% ammonium hydroxide, 40% ammonium sulfate and pure water are that the ratio of 5:10:10 is mixed with by volume, and aluminum solutions are molten by aluminium dioxide
It is prepared in mixed acid, mixed acid is mixed to get by the ratio that 37% hydrochloric acid and 60% nitric acid are 2:0.5 by volume, and aluminium is molten
The pH of liquid is controlled less than 0.5, and following reaction occurs:
The mass concentration of aluminium is 0.015g/L in aluminium-complex liquid mixed solution.
In S1, aluminum solutions are added in compound complex liquid and prepare aluminium-complex liquid mixed solution, aluminium-complex liquid mixing is molten
The mass concentration of aluminium is 0.015g/L in liquid, and the cobalt source for preparing cobalt liquor is cobalt salt, and cobalt salt uses cobalt nitrate, cobalt chloride and sulfuric acid
At least one of cobalt, concentration of cobalt ions is 80g/L in cobalt liquor, and the naoh concentration in liquid alkaline solution is 2.5mol/L.
Reaction kettle is added from reaction kettle side cocurrent, by liquid alkaline in cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution by S2
Reaction kettle is added from the reaction kettle other side with metering method in solution；
In S2, cobalt liquor, ammonium hydroxide and aluminium-complex liquid are passed through after constant displacement pump quantitatively conveys by parallel pipeline respectively from reaction kettle
Bottom be sent in reaction kettle.
In S2, by solubility be 1% liquid alkaline solution in such a way that finished product metering pump quantitatively conveys from the upper of reaction kettle
In side's spray to reaction kettle, controlling the temperature in reaction kettle is 40 DEG C.
In S2, the flow-rate ratio of cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution and liquid alkaline solution is 1:0.1, entirely
Following reaction occurs for process:
。
S3 is stirred by the solution that auger impeller will be added in reaction kettle, and the pH value for controlling solution is big
About 12.4；
In S3, agitator arm carries out centrifugal mixer to the reaction solution in reaction kettle with the stirring rate of 50r/min, is stirring
While into reaction kettle supplying nitrogen.
S4, the solution stand that will be uniformly mixed in reaction kettle, by supernatant liquid filtering into aging tank；
In S4, supernatant precipitation solution is filtered by the solution stand 30min in reaction kettle, leave and take filter D50 be 6um
Reaction solution, the reaction solution filtered out continues to employ as the bottom liquid of reaction kettle secondary response, and the time of ageing is 45min,.
Reactant after ageing is sintered and is mixed and criticized except magnetic treatment, obtained finished product and mix alumina cobalt precursor by S5.
In S5, sintering and the mixed batch of time for removing magnetic treatment are 6h, and sintering process uses three-stage sintering, first segment sintering temperature
Degree is 200 DEG C, and the time is 1 hour, and second segment sintering temperature is 450 DEG C, and the time is 2 hours, and third section burns sintering junction temperature and is
650 DEG C, the time is 3 hours, and following reaction occurs:
。
Since aluminium ion is present in peracidity aqueous solution, prepared if be blended using solids ratios, entire molten metal is all
Highly acid can be presented, when squeezing into reaction kettle, meeting severe jamming reaction kettle synthesis condition, so aluminium ion can only be individually prepared
At aqueous solution；Saturation degree control problem seeks to reduce degree of supersaturation, concrete operation method are as follows: adopt specific to the control of Ti4+
Part aluminium ion is complexed into aluminium complex ion with the method for complexing agent, reaches complexation equilibrium in the solution, ion is greatly reduced
State aluminium selects suitable complex system, and aluminum ions degree of supersaturation is enabled to match the degree of supersaturation of main metal, reaches homogeneous
Co-precipitation.
It really realizes that even aluminium doping introduces the precedent of synthesis presoma currently without in reaction kettle, there is mixed method synthesis forerunner
It is mixed with aluminium in body, but is the doping precursor synthesis elder generation for being directly proportionally pumped into reaction kettle formation with alumina in Nano level
Example can not accomplish the microcosmic uniform presoma adulterated using nano aluminium oxide, be viewed as " Glutinous rice sesame balls " pattern under Electronic Speculum,
But can greatly also improve the sintering strength for mixing aluminium, it is spread after all relative to high temperature solid-state outside bulky grain, nanoscale oxygen
Change aluminium, which has had, is largely distributed in presoma intrinsic silicon.
Aluminium presoma is mixed using the synthesis of this patent technique, the homogeneous shown as under Electronic Speculum entirely without obvious second phase is coprecipitated
Shallow lake state, hence it is evident that be better than nano aluminium oxide doping type presoma.Aluminium lithium ion anode material is mixed using present invention process synthesis
Presoma, aluminium element are uniformly distributed in presoma, show as being co-precipitated state entirely without the homogeneous of obvious second phase under Electronic Speculum,
It is substantially better than nano aluminium oxide doping type presoma, mixes the same of aluminium lithium ion anode material presoma intensity prepared by guaranteeing
When, prepared aluminium element is uniformly distributed in that presoma is more uniform, effectively compensates for the defect of the prior art, has good
Practicability.
Embodiment 2
As shown in attached drawing 1-2, the present embodiment provides a kind of preparation method for mixing aluminium lithium ion anode material presoma, including it is following
Step:
It is spare to prepare cobalt liquor, liquid alkaline solution, aluminium-complex liquid mixed solution by S1；
In S1, the aluminium-complex liquid mixed solution is mixed with by compound complex liquid and aluminum solutions, compound complex liquid by
20% ammonium hydroxide, 40% ammonium sulfate and pure water are that the ratio of 7.5:10:10 is mixed with by volume, and aluminum solutions are by aluminium dioxide
It is dissolved in mixed acid and being prepared, mixed acid is mixed to get by the ratio that 37% hydrochloric acid and 60% nitric acid are 3:1 by volume, and aluminium is molten
The pH of liquid is controlled less than 0.5, and following reaction occurs:
The mass concentration of aluminium is 0.565g/L in aluminium-complex liquid mixed solution.
In S1, aluminum solutions are added in compound complex liquid and prepare aluminium-complex liquid mixed solution, aluminium-complex liquid mixing is molten
The mass concentration of aluminium is 0.565g/L in liquid, and the cobalt source for preparing cobalt liquor is cobalt salt, and cobalt salt uses cobalt nitrate, cobalt chloride and sulfuric acid
At least one of cobalt, concentration of cobalt ions is 100g/L in cobalt liquor, and the naoh concentration in liquid alkaline solution is 3.25mol/
L。
Reaction kettle is added from reaction kettle side cocurrent, by liquid alkaline in cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution by S2
Reaction kettle is added from the reaction kettle other side with metering method in solution；
In S2, cobalt liquor, ammonium hydroxide and aluminium-complex liquid are passed through after constant displacement pump quantitatively conveys by parallel pipeline respectively from reaction kettle
Bottom be sent in reaction kettle.
In S2, by solubility be 3% liquid alkaline solution in such a way that finished product metering pump quantitatively conveys from the upper of reaction kettle
In side's spray to reaction kettle, controlling the temperature in reaction kettle is 60 DEG C.
In S2, the flow-rate ratio of cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution and liquid alkaline solution is 1:0.5, entirely
Following reaction occurs for process:
。
S3 is stirred by the solution that auger impeller will be added in reaction kettle, and the pH value for controlling solution is big
About 12.4；
In S3, agitator arm carries out centrifugal mixer to the reaction solution in reaction kettle with the stirring rate of 125r/min, is stirring
While mixing into reaction kettle supplying nitrogen.
S4, the solution stand that will be uniformly mixed in reaction kettle, by supernatant liquid filtering into aging tank；
In S4, supernatant precipitation solution is filtered by the solution stand 60min in reaction kettle, leave and take filter D50 be 12um
Reaction solution, the reaction solution filtered out continues to employ as the bottom liquid of reaction kettle secondary response, and the time of ageing is 70min,.
Reactant after ageing is sintered and is mixed and criticized except magnetic treatment, obtained finished product and mix alumina cobalt precursor by S5.
In S5, sintering and the mixed batch of time for removing magnetic treatment are 7.5h, and sintering process uses three-stage sintering, first segment sintering
Temperature is 275 DEG C, and the time is 2 hours, and second segment sintering temperature is 475 DEG C, and the time is 3.5 hours, and third section burns sintering junction temperature
Degree is 700 DEG C, and the time is 4.5 hours, and following reaction occurs:
。
Since aluminium ion is present in peracidity aqueous solution, prepared if be blended using solids ratios, entire molten metal is all
Highly acid can be presented, when squeezing into reaction kettle, meeting severe jamming reaction kettle synthesis condition, so aluminium ion can only be individually prepared
At aqueous solution；Saturation degree control problem seeks to reduce degree of supersaturation, concrete operation method are as follows: adopt specific to the control of Ti4+
Part aluminium ion is complexed into aluminium complex ion with the method for complexing agent, reaches complexation equilibrium in the solution, ion is greatly reduced
State aluminium selects suitable complex system, and aluminum ions degree of supersaturation is enabled to match the degree of supersaturation of main metal, reaches homogeneous
Co-precipitation.
It really realizes that even aluminium doping introduces the precedent of synthesis presoma currently without in reaction kettle, there is mixed method synthesis forerunner
It is mixed with aluminium in body, but is the doping precursor synthesis elder generation for being directly proportionally pumped into reaction kettle formation with alumina in Nano level
Example can not accomplish the microcosmic uniform presoma adulterated using nano aluminium oxide, be viewed as " Glutinous rice sesame balls " pattern under Electronic Speculum,
But can greatly also improve the sintering strength for mixing aluminium, it is spread after all relative to high temperature solid-state outside bulky grain, nanoscale oxygen
Change aluminium, which has had, is largely distributed in presoma intrinsic silicon.
Aluminium presoma is mixed using the synthesis of this patent technique, the homogeneous shown as under Electronic Speculum entirely without obvious second phase is coprecipitated
Shallow lake state, hence it is evident that be better than nano aluminium oxide doping type presoma.Aluminium lithium ion anode material is mixed using present invention process synthesis
Presoma, aluminium element are uniformly distributed in presoma, show as being co-precipitated state entirely without the homogeneous of obvious second phase under Electronic Speculum,
It is substantially better than nano aluminium oxide doping type presoma, mixes the same of aluminium lithium ion anode material presoma intensity prepared by guaranteeing
When, prepared aluminium element is uniformly distributed in that presoma is more uniform, effectively compensates for the defect of the prior art, has good
Practicability.
Embodiment 3
The present embodiment provides a kind of preparation methods for mixing aluminium lithium ion anode material presoma, comprising the following steps:
As shown in attached drawing 1-2, a kind of preparation method for mixing aluminium lithium ion anode material presoma, specifically includes the following steps:
It is spare to prepare cobalt liquor, liquid alkaline solution, aluminium-complex liquid mixed solution by S1；
In S1, the aluminium-complex liquid mixed solution is mixed with by compound complex liquid and aluminum solutions, compound complex liquid by
20% ammonium hydroxide, 40% ammonium sulfate and pure water are that the ratio of 7.5:15:10 is mixed with by volume, and aluminum solutions are by aluminium dioxide
It is dissolved in mixed acid and being prepared, mixed acid is mixed to get by the ratio that 37% hydrochloric acid and 60% nitric acid are 4:1.5 by volume, aluminium
The pH of solution is controlled less than 0.5, and following reaction occurs:
The mass concentration of aluminium is 1.1g/L in aluminium-complex liquid mixed solution.
In S1, aluminum solutions are added in compound complex liquid and prepare aluminium-complex liquid mixed solution, aluminium-complex liquid mixing is molten
The mass concentration of aluminium is 1.1g/L in liquid, and the cobalt source for preparing cobalt liquor is cobalt salt, and cobalt salt uses cobalt nitrate, cobalt chloride and cobaltous sulfate
At least one of, concentration of cobalt ions is 120g/L in cobalt liquor, and the naoh concentration in liquid alkaline solution is 4mol/L.
Reaction kettle is added from reaction kettle side cocurrent, by liquid alkaline in cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution by S2
Reaction kettle is added from the reaction kettle other side with metering method in solution；
In S2, cobalt liquor, ammonium hydroxide and aluminium-complex liquid are passed through after constant displacement pump quantitatively conveys by parallel pipeline respectively from reaction kettle
Bottom be sent in reaction kettle.
In S2, by solubility be 5% liquid alkaline solution in such a way that finished product metering pump quantitatively conveys from the upper of reaction kettle
In side's spray to reaction kettle, controlling the temperature in reaction kettle is 40-80 DEG C.
In S2, the flow-rate ratio of cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution and liquid alkaline solution is 1:10, entirely
Following reaction occurs for process:
。
S3 is stirred by the solution that auger impeller will be added in reaction kettle, and the pH value for controlling solution is big
About 12.4；
In S3, agitator arm carries out centrifugal mixer to the reaction solution in reaction kettle with the stirring rate of 200r/min, is stirring
While mixing into reaction kettle supplying nitrogen.
S4, the solution stand that will be uniformly mixed in reaction kettle, by supernatant liquid filtering into aging tank；
In S4, supernatant precipitation solution is filtered by the solution stand 90min in reaction kettle, leave and take filter D50 be 18um
Reaction solution, the reaction solution filtered out continues to employ as the bottom liquid of reaction kettle secondary response, and the time of ageing is 90min,.
Reactant after ageing is sintered and is mixed and criticized except magnetic treatment, obtained finished product and mix alumina cobalt precursor by S5.
In S5, sintering and the mixed batch of time for removing magnetic treatment are 9h, and sintering process uses three-stage sintering, first segment sintering temperature
Degree is 350 DEG C, and the time is 3 hours, and second segment sintering temperature is 500 DEG C, and the time is 5 hours, and third section burns sintering junction temperature and is
750 DEG C, the time is 6 hours, and following reaction occurs:
。
Since aluminium ion is present in peracidity aqueous solution, prepared if be blended using solids ratios, entire molten metal is all
Highly acid can be presented, when squeezing into reaction kettle, meeting severe jamming reaction kettle synthesis condition, so aluminium ion can only be individually prepared
At aqueous solution；Saturation degree control problem seeks to reduce degree of supersaturation, concrete operation method are as follows: adopt specific to the control of Ti4+
Part aluminium ion is complexed into aluminium complex ion with the method for complexing agent, reaches complexation equilibrium in the solution, ion is greatly reduced
State aluminium selects suitable complex system, and aluminum ions degree of supersaturation is enabled to match the degree of supersaturation of main metal, reaches homogeneous
Co-precipitation.
It really realizes that even aluminium doping introduces the precedent of synthesis presoma currently without in reaction kettle, there is mixed method synthesis forerunner
It is mixed with aluminium in body, but is the doping precursor synthesis elder generation for being directly proportionally pumped into reaction kettle formation with alumina in Nano level
Example can not accomplish the microcosmic uniform presoma adulterated using nano aluminium oxide, be viewed as " Glutinous rice sesame balls " pattern under Electronic Speculum,
But can greatly also improve the sintering strength for mixing aluminium, it is spread after all relative to high temperature solid-state outside bulky grain, nanoscale oxygen
Change aluminium, which has had, is largely distributed in presoma intrinsic silicon.
Aluminium presoma is mixed using the synthesis of this patent technique, the homogeneous shown as under Electronic Speculum entirely without obvious second phase is coprecipitated
Shallow lake state, hence it is evident that be better than nano aluminium oxide doping type presoma.Aluminium lithium ion anode material is mixed using present invention process synthesis
Presoma, aluminium element are uniformly distributed in presoma, show as being co-precipitated state entirely without the homogeneous of obvious second phase under Electronic Speculum,
It is substantially better than nano aluminium oxide doping type presoma, mixes the same of aluminium lithium ion anode material presoma intensity prepared by guaranteeing
When, prepared aluminium element is uniformly distributed in that presoma is more uniform, effectively compensates for the defect of the prior art, has good
Practicability.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method for mixing aluminium lithium ion anode material presoma, it is characterised in that include the following steps:
It is spare to prepare cobalt liquor, liquid alkaline solution, aluminium-complex liquid mixed solution by S1；
Reaction kettle is added from reaction kettle side cocurrent, by liquid alkaline solution in cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution by S2
Reaction kettle is added from the reaction kettle other side with metering method；
S3 is stirred by the solution that auger impeller will be added in reaction kettle, and controls the pH value of solution about
12.4；
S4, the solution stand that will be uniformly mixed in reaction kettle, by supernatant liquid filtering into aging tank；
Reactant after ageing is sintered and is mixed and criticized except magnetic treatment, obtained finished product and mix alumina cobalt precursor by S5.
2. a kind of preparation method for mixing aluminium lithium ion anode material presoma according to claim 1, which is characterized in that
In S1, the aluminium-complex liquid mixed solution is mixed with by compound complex liquid and aluminum solutions, and compound complex liquid is by 20% ammonia
Water, 40% ammonium sulfate and pure water are that 5~10:10~15:10 ratio is mixed with by volume, and aluminum solutions are by titanium dioxide
Aluminium, which is dissolved in mixed acid, to be prepared, and mixed acid is the ratio of 2~4:0.5~1.5 by 37% hydrochloric acid and 60% nitric acid by volume
It is mixed to get, the pH of aluminum solutions is controlled less than 0.5.
3. a kind of preparation method for mixing aluminium lithium ion anode material presoma according to claim 2, which is characterized in that
In S1, aluminum solutions are added in compound complex liquid and prepare aluminium-complex liquid mixed solution, the matter of aluminium in aluminium-complex liquid mixed solution
Amount concentration is 0.015~1.1g/L, and the cobalt source for preparing cobalt liquor is cobalt salt, and cobalt salt is using in cobalt nitrate, cobalt chloride and cobaltous sulfate
At least one, concentration of cobalt ions is 80-120g/L in cobalt liquor, and the naoh concentration in liquid alkaline solution is 2.5~4mol/
L。
4. a kind of preparation method for mixing aluminium lithium ion anode material presoma according to claim 1-3, special
Sign is, in S2, cobalt liquor, ammonium hydroxide and aluminium-complex liquid are passed through after constant displacement pump quantitatively conveys by parallel pipeline respectively from anti-
The bottom of kettle is answered to be sent in reaction kettle.
5. a kind of preparation method for mixing aluminium lithium ion anode material presoma according to claim 4, which is characterized in that
In S2, by solubility be 1-5% liquid alkaline solution in such a way that finished product metering pump quantitatively conveys from the top of reaction kettle spray to
In reaction kettle, controlling the temperature in reaction kettle is 40-80 DEG C.
6. a kind of preparation method for mixing aluminium lithium ion anode material presoma according to claim 5, which is characterized in that
In S2, the flow-rate ratio of cobalt liquor, ammonium hydroxide and aluminium-complex liquid mixed solution and liquid alkaline solution is 1:(0.1-10).
7. a kind of preparation method for mixing aluminium lithium ion anode material presoma according to claim 6, which is characterized in that
In S3, agitator arm carries out centrifugal mixer to the reaction solution in reaction kettle with the stirring rate of 50-200r/min, in stirring
The supplying nitrogen into reaction kettle simultaneously.
8. a kind of preparation method for mixing aluminium lithium ion anode material presoma according to claim 7, which is characterized in that
In S4, supernatant precipitation solution is filtered by the solution stand 30-90min in reaction kettle, leave and take filter D50 be 6-18um
Reaction solution, the reaction solution filtered out continues to employ as the bottom liquid of reaction kettle secondary response.
9. a kind of preparation method for mixing aluminium lithium ion anode material presoma according to claim 8, which is characterized in that
In S5, sintering process uses three-stage sintering, and first segment sintering temperature is 200~350 DEG C, and the time is 1-3 hours, second segment sintering
Temperature is 450~500 DEG C, and the time is 2~5 hours, and third section sintering junction temperature is 650-750 DEG C, and the time is 3~6 hours.
10. a kind of preparation method for mixing aluminium lithium ion anode material presoma according to claim 9, which is characterized in that
In S4, the time of ageing is 45-90min, and in S5, sintering and the mixed batch of time for removing magnetic treatment are 6-9h.
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