A kind of spherical Lithii carbonate and preparation method thereof
Technical field
The invention belongs to lithium carbonate preparing technical field, more particularly, is related to a kind of ball-type lithium carbonate and its preparation side
Method.
Background technology
Lithium carbonate is the important source material of fine chemistry industry production, is widely used in glass, ceramics, electronics industry, aluminium metallurgy and pharmacy
Etc. industry, it is the important source material for producing other lithium compounds and lithium metal.
The basic material of carbonic acid reason or manufacture lithium ion battery.In recent years, it is big with power vehicle and energy-storage battery
Scale breaks out, and lithium carbonate applies accounting in terms of battery also more and more higher.Lithium carbonate in the application of battery, its granularity and point
Impact of the scattered property to application performance is very big.Such as prepared in LiFePO4 technical process using solid-phase synthesis, with iron phosphate or its
Its phosphorus, source of iron are raw material, add lithium carbonate and other adjuvants to be sintered after being sufficiently mixed and obtain LiFePO 4 material.Mobility
Then it is possible to, in other supplementary material surface non-homogeneous dispersions, cause the concordance of product bad with the lithium carbonate of poor dispersion.
Document《The Study on Preparation of spherical fine carbonic acid powder for lithium》There is provided a kind of system of nanoscale ball-type lithium carbonate
Preparation Method.The method is with technical grade LiOH H2O and NH4HCO3For raw material, react 20min under the conditions of 40 DEG C, gained solid in
200 DEG C are dried 1h and obtain carbonic acid powder for lithium, and its granularity is 300~400nm.
But, the method is suffered from the drawback that:1st, Lithium hydrate is adopted to prepare lithium carbonate for raw material, high cost and yield is low
(market price of Lithium hydrate is higher than lithium carbonate);2nd, there are ammonia and the water containing ammonium ion to produce in production process, ring can be endangered
Border and worker health, are unfavorable for industrialized production.
The content of the invention
In order to solve problems of the prior art, it is an object of the invention to provide a kind of low cost, purity are high, more sharp
In more excellent ball-type lithium carbonate of industrialized production and environmental conservation and effect and preparation method thereof.
An aspect of of the present present invention provides the preparation method of spherical Lithii carbonate, and the preparation method is comprised the following steps:
A, preparation sodium carbonate liquor and lithium sulfate solution;
B, add in sodium carbonate liquor or lithium sulfate solution and surface conditioning agent stir;
C, under high-speed stirred state, lithium sulfate solution and sodium carbonate liquor are mixed, controlling reaction temperature is 50
~100 DEG C;
D, insulation ageing is carried out under stirring at low speed state, material solid-liquid separation is obtained into lithium carbonate wet product and sinker is female
Liquid;
E, the lithium carbonate wet product is washed and spherical Lithii carbonate is obtained after being dried.
According to one embodiment of the preparation method of spherical Lithii carbonate of the present invention, in step, the sodium carbonate liquor
Concentration is 100~350g/L, and the concentration of the lithium sulfate solution is with Li2O is calculated as 10~65g/L, sodium carbonate liquor and lithium sulfate
The amount of solution presses CO3 2-With Li2The mol ratio of O is 0.9~1.1 control.
According to one embodiment of the preparation method of spherical Lithii carbonate of the present invention, the surface conditioning agent be triethanolamine,
At least one in sodium lauryl sulphate and sodium carboxymethyl cellulose.
According to one embodiment of the preparation method of spherical Lithii carbonate of the present invention, wherein, the surface conditioning agent is with water-soluble
The mode of liquid add and surface conditioning agent aqueous solution concentration be 1~5g/L, the addition of the surface conditioning agent aqueous solution
For overall solution volume 1 ‰~5 ‰.
According to one embodiment of the preparation method of spherical Lithii carbonate of the present invention, in step C, the high-speed stirred state
Under mixing speed be 150~2000r/min, feed time be 1.5~2.5h.
According to one embodiment of the preparation method of spherical Lithii carbonate of the present invention, the carbonic acid before surface conditioning agent will be added
Sodium solution and lithium sulfate solution or sodium carbonate liquor and lithium sulfate solution after addition surface conditioning agent are warming up to 50~100
DEG C reaching the reaction temperature in step C.
According to one embodiment of the preparation method of spherical Lithii carbonate of the present invention, in step D, the stirring at low speed state
Under mixing speed be 30~60r/min, insulation Aging Temperature be 50~100 DEG C, insulation digestion time be 30~120min.
According to one embodiment of the preparation method of spherical Lithii carbonate of the present invention, in step E, baking temperature be 110~
220 DEG C, drying time is 2~4h.
A kind of spherical Lithii carbonate is another aspect provides, using the preparation method system of above-mentioned spherical Lithii carbonate
.
According to one embodiment of spherical Lithii carbonate of the present invention, the purity of the spherical Lithii carbonate is more than 99.5wt%
And grain shape is spherical or elliposoidal, mean diameter D50 is 2~10 μm.
The present invention with spodumene prepare lithium sulfate solution and technical grade sodium carbonate prepare solution as raw material, by control
Process conditions, add surface conditioning agent to obtain spherical Lithii carbonate of the purity more than 99.5%, the purity of gained spherical Lithii carbonate compared with
It is high and be difficult to reunite, with good mobility and dispersibility, be conducive to batch mixing and the processing of subsequent technique.
Description of the drawings
Fig. 1 shows the process chart of the preparation method of spherical Lithii carbonate according to an exemplary embodiment of the present invention.
Specific embodiment
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine by any way.
Any feature disclosed in this specification, unless specifically stated otherwise, can be equivalent or with similar purpose by other
Alternative features are replaced.I.e., unless specifically stated otherwise, each feature is an example in a series of equivalent or similar characteristics
.
First the principle and step of the preparation method of spherical Lithii carbonate of the present invention are described in detail below.The present invention is
With spodumene prepare lithium sulfate solution and technical grade sodium carbonate prepare sodium carbonate liquor as raw material, by control process conditions
And add surface conditioning agent to obtain spherical Lithii carbonate of the purity more than 99.5%, can effectively substitute side of the prior art
Method, and prepare the spherical Lithii carbonate of alternative currently marketed micropowder battery-level lithium carbonate.
Fig. 1 shows the process chart of the preparation method of spherical Lithii carbonate according to an exemplary embodiment of the present invention.Such as
Shown in Fig. 1, exemplary embodiment of the invention, the preparation method of the spherical Lithii carbonate include following multiple steps.
Step A:
Prepare sodium carbonate liquor and lithium sulfate solution.
Wherein, lithium sulfate solution is prepared with spodumene, and sodium carbonate liquor is to be prepared to obtain by technical grade sodium carbonate
Clear solution.Preferably, control the Ca in lithium sulfate solution2+<0.01g/L and pH value are 7~12.
Specifically, the concentration of sodium carbonate liquor is 100~350g/L, and the concentration of lithium sulfate solution is with Li2O is calculated as 10~
The amount of 65g/L, sodium carbonate liquor and lithium sulfate solution presses CO3 2-With Li2The mol ratio of O is 0.9~1.1 control.
Step B:
Surface conditioning agent is added in sodium carbonate liquor or lithium sulfate solution and is stirred.
Preferably, the surface conditioning agent that the present invention is selected is triethanolamine, sodium lauryl sulphate and carboxymethyl cellulose
At least one in sodium, the addition of surface conditioning agent can prevent crystal grain from growing up and make lithium carbonate granule uniform and narrow particle size distribution.
Wherein, surface conditioning agent can add the mix homogeneously into sodium carbonate liquor, it is also possible to add to lithium sulfate solution
Middle mix homogeneously, but be preferably added in sodium carbonate liquor.
Specifically, surface conditioning agent can be added in the way of aqueous solution and surface conditioning agent aqueous solution concentration as 1
~5g/L, the addition of the surface conditioning agent aqueous solution is 1 ‰~the 5 ‰ of overall solution volume.
Step C:
Under high-speed stirred state, lithium sulfate solution and sodium carbonate liquor are mixed, preferably by lithium sulfate solution
It is slowly added to into sodium carbonate liquor until add, wherein, controlling reaction temperature is 50~100 DEG C.
This step is the committed step of the present invention, and controlling reaction temperature is 50~100 DEG C, can maintain the work of reaction system
Property, increase extent of reaction, while reducing impurity parcel, have larger benefit to improving product purity.During practical operation, will can add
Sodium carbonate liquor and lithium sulfate solution before entering surface conditioning agent is warming up to 50~100 DEG C, it is also possible to will add surface treatment
Sodium carbonate liquor and lithium sulfate solution after agent is warming up to 50~100 DEG C, so as to reach the reaction temperature in step C.
Preferably, it is 150~2000r/min to control the mixing speed under high-speed stirred state.Mixing speed is controlled for 150
The fair speed of~2000r/min, after making reaction, the lithium carbonate of strip pattern to be formed generates length in the case where constantly colliding originally
Wide ratio be close to granule and make Pedicellus et Pericarpium Trapae be collided smooth, the spherical Lithii carbonate granule higher so as to obtain quality.
It is further preferred that controlling feed time for 1.5~2.5h.The purpose of control feed time is suitable in order to control
Charging rate, to feed and can extend the response time slowly, reduce the unit interval yield, increase production cost;Charging rate mistake
Fast then degree of supersaturation of in reaction system is too high, easily wraps up impurity, reduces product purity, meanwhile, it is also easy to produce short grained product
Product and occur it is soft-agglomerated, affect product pattern and correlation physical property.
Step D:
Insulation ageing is carried out under stirring at low speed state, material solid-liquid separation is obtained into lithium carbonate wet product and sinker mother solution.
Preferably, it is 30~60r/min to control the mixing speed under stirring at low speed state.Control the stirring speed in this step
Spend for relatively low speed, have during product can be made the granule of lattice defect gradually it is long it is brilliant repair, obtain the more perfect product of crystal formation.
It is further preferred that it is 30~120min to control to be incubated Aging Temperature for 50~100 DEG C and be incubated digestion time.Instead
Should after the completion of, by mixture insulation 30~120min of ageing, advantageously form perfect crystal formation, and obtain that shape is more regular and quality
More excellent spherical Lithii carbonate.
Step E:
Lithium carbonate wet product is washed and spherical Lithii carbonate is obtained after being dried.
Wherein, baking temperature is controlled 110~220 DEG C and drying time to be 2~4h.
The spherical Lithii carbonate that the present invention is provided is obtained using the preparation method of above-mentioned spherical Lithii carbonate.Specifically, originally
The purity of the spherical Lithii carbonate that invention is prepared is more than 99.5wt% and grain shape is that spherical or elliposoidal etc. is subsphaeroidal, puts down
Particle diameter D50 is 2~10 μm.
The spherical Lithii carbonate that the present invention is prepared can substitute currently marketed micropowder battery-level lithium carbonate, and by
There is more preferable mobility relative to micropowder lithium carbonate in the spherical Lithii carbonate of the present invention, therefore to improving powder reuniting, extending
There is in terms of shelf-life positive effect, also there is positive meaning to reducing battery synthesis sintering energy consumption, while may be to carrying
High battery performance has certain beneficial effect.Additionally, the equipment of the microreactor in the face of flourishing, using spherical Lithii carbonate
The generation of plugging phenomenon is effectively reduced or is eliminated, is had a good application prospect.
It should be understood that the above-mentioned embodiment and following examples of present invention detailed description are merely to illustrate the present invention rather than limit
The scope of the present invention processed, some nonessential improvement and tune that those skilled in the art's the above of the invention is made
It is whole to belong to protection scope of the present invention.
Spherical Lithii carbonate of the invention and preparation method thereof is described further with reference to specific embodiment.
Embodiment 1:
Concentration is pipetted with Li2O is calculated as the lithium sulfate solution 1500mL of 55g/L, controls Ca2+<0.01g/L, pH are 7~12;
Weigh during 310g technical grade sodium carbonate is dissolved in 1000mL hot water and be filtered to remove insoluble matter.Sodium carbonate liquor is transferred to into 3L appearances
In device and 50 DEG C are heated to, add sodium carboxymethyl cellulose solution (advance compound concentration is 1g/L) 3mL, control mixing speed
For 2000r/min, lithium sulfate solution is slowly dropped in sodium carbonate liquor, charging rate is controlled for 17mL/min.
After having fed, continue insulation at 50 DEG C, it is 30r/min to control mixing speed, stops stirring after insulation ageing 30min
Mix, material is carried out rapidly solid-liquid separation, then by gained lithium carbonate wet product abundant drip washing and 4h is dried at 110 DEG C and obtains ball
Shape lithium carbonate product, the performance data of product are as shown in table 1 below.
The spherical Lithii carbonate properties of product data that 1 embodiment 1 of table is prepared
Embodiment 2:
Concentration is pipetted with Li2O is calculated as the lithium sulfate solution 5000mL of 55g/L, controls Ca2+<0.01g/L, pH are 7~12;
Weigh during 1033g technical grade sodium carbonate is dissolved in 3440mL hot water and be filtered to remove insoluble matter.Sodium carbonate liquor is transferred to into 10L
In container and 100 DEG C are heated to, add triethanolamine aqueous solution (advance compound concentration is 2g/L) 10mL, controlling mixing speed is
1000r/min, lithium sulfate solution is slowly dropped in sodium carbonate liquor, controls charging rate for 50mL/min.
After having fed, continue insulation at 100 DEG C, it is 40r/min to control mixing speed, stops stirring after insulation ageing 60min
Mix, material is carried out rapidly solid-liquid separation, then by gained lithium carbonate wet product abundant drip washing and 2h is dried in 220 DEG C and obtains spherical
Lithium carbonate product, the performance data of product are as shown in table 2 below.
The spherical Lithii carbonate properties of product data that 2 embodiment 2 of table is prepared
Embodiment 3:
Concentration is pipetted with Li2O is calculated as the lithium sulfate solution 10L of 55g/L, controls Ca2+<0.01g/L, pH are 7~12;Weigh
During 2065g technical grade sodium carbonate is dissolved in 6880mL hot water and it is filtered to remove insoluble matter.Sodium carbonate liquor is transferred to into 20L containers
In and be heated to 95 DEG C, add sodium carboxymethyl cellulose solution (advance compound concentration be 1g/L) 15mL, control mixing speed
For 500r/min, lithium sulfate solution is slowly dropped in sodium carbonate liquor, charging rate is controlled for 91mL/min.
After having fed, continue insulation at 90 DEG C, it is 50r/min to control mixing speed, stops stirring after insulation ageing 90min
Mix, material is carried out rapidly solid-liquid separation, then by gained lithium carbonate wet product abundant drip washing and 4h is dried in 110 DEG C and obtains spherical
Lithium carbonate product, the performance data of product are as shown in table 3 below.
The spherical Lithii carbonate properties of product data that 3 embodiment 3 of table is prepared
Embodiment 4:
Concentration is pipetted with Li2O is calculated as the lithium sulfate solution 100L of 55g/L, controls Ca2+<0.01g/L, pH are 7~12;Claim
Take during 21Kg technical grade sodium carbonate is dissolved in 70L hot water and be filtered to remove insoluble matter.Sodium carbonate liquor is transferred to into 200L containers
In and be heated to 95 DEG C, add sodium dodecyl sulfate aqueous solution (advance compound concentration be 1g/L) 200mL, control mixing speed
For 500r/min, lithium sulfate solution is slowly dropped in sodium carbonate liquor, charging rate is controlled for 850mL/min.
After having fed, continue insulation at 90 DEG C, it is 60 turns/min to control mixing speed, stops stirring after insulation ageing 90min
Mix, material is carried out rapidly solid-liquid separation, then fully drip washing., then by gained lithium carbonate wet product abundant drip washing and in 220 DEG C
Under be dried 2h and obtain spherical Lithii carbonate product, the performance data of product is as shown in table 4 below.
The spherical Lithii carbonate properties of product data that 4 embodiment 4 of table is prepared
Embodiment 5:
Concentration is pipetted with Li2O is calculated as the lithium sulfate solution 1000L of 55g/L, controls Ca2+<0.01g/L, pH are 7~12;Claim
Take during 21Kg technical grade sodium carbonate is dissolved in 70L hot water and be filtered to remove insoluble matter.Sodium carbonate liquor is transferred to into 2000L containers
In and be heated to 95 DEG C, add triethanolamine aqueous solution (advance compound concentration be 2g/L) 2000mL, controlling mixing speed is
150r/min, lithium sulfate solution is slowly dropped in sodium carbonate liquor, controls charging rate for 7700mL/min.
After having fed, continue insulation at 90 DEG C, maintenance mixing speed is 60r/min, stops stirring after insulation ageing 60min
Mix, material is carried out rapidly solid-liquid separation, then by gained lithium carbonate wet product abundant drip washing and 2h is dried in 220 DEG C and obtains spherical
Lithium carbonate product, the performance data of product are as shown in table 5 below.
The spherical Lithii carbonate properties of product data that 5 embodiment 5 of table is prepared
Embodiment 6:
Concentration is pipetted with Li2O is calculated as the lithium sulfate solution 1000L of 55g/L, controls Ca2+<0.01g/L, pH are 7~12;Claim
Take during 21Kg technical grade sodium carbonate is dissolved in 70L hot water and be filtered to remove insoluble matter.Sodium carbonate liquor is transferred to into 2000L containers
In and be heated to 95 DEG C, add sodium dodecyl sulfate aqueous solution (advance compound concentration be 1g/L) 2000mL, control stirring speed
Spend for 300r/min, lithium sulfate solution is slowly dropped in sodium carbonate liquor, charging rate is controlled for 6700mL/min.
After having fed, continue insulation at 90 DEG C, it is 45r/min to control mixing speed, stops stirring after insulation ageing 120min
Mix, material is carried out rapidly solid-liquid separation, then by gained lithium carbonate wet product abundant drip washing and 4h is dried in 110 DEG C and obtains spherical
Lithium carbonate product, the performance data of product are as shown in table 6 below.
The spherical Lithii carbonate properties of product data that 6 embodiment 6 of table is prepared
Embodiment 7:
Concentration is pipetted with Li2O is calculated as the lithium sulfate solution 5000mL of 55g/L, controls Ca2+<0.01g/L, pH are 7~12;
Weigh during 1033g technical grade sodium carbonate is dissolved in 3440L hot water and be filtered to remove insoluble matter.Sodium carbonate liquor is transferred to into 10L
In container and 95 DEG C are heated to, add sodium dodecyl sulfate aqueous solution (advance compound concentration is 1g/L) 9mL, control stirring speed
Spend for 150r/min, lithium sulfate solution is slowly dropped in sodium carbonate liquor, charging rate is controlled for 50mL/min.
After having fed, continue insulation at 90 DEG C, it is 50r/min to control mixing speed, stops stirring after insulation ageing 120min
Mix, material is carried out rapidly solid-liquid separation, then by gained lithium carbonate wet product abundant drip washing and 4h is dried in 110 DEG C and obtains spherical
Lithium carbonate product, the performance data of product are as shown in table 7 below.
The spherical Lithii carbonate properties of product data that 7 embodiment 7 of table is prepared
Comparison and detection data:
Micropowder refers to the lithium carbonate prepared with conventional method, by micropowder lithium carbonate product obtained in comminution by gas stream.Embodiment refers to
The spherical Lithii carbonate for preparing in the process of the present invention.Comparing result is as shown in table 8.
The performance comparison of the spherical Lithii carbonate of 8 existing micropowder lithium carbonate of table and the present invention
From the data of table 1 to table 8, micropowder lithium carbonate prepared by airbrasive technique is nearly cuboid, using the inventive method
The lithium carbonate for preparing is ball-type or nearly ball-type, affects Flow of Goods and Materials in mass velocity, the degree of compression, angle of repose, voidage etc.
Property in terms of important indicator be superior to airbrasive technique preparation micropowder lithium carbonate.The size of particle diameter can be by adjusting process parameter
Controlled, material has more preferable mobility, therefore there is positive work to improving powder reuniting, the aspect that extends the shelf life
With, to reduce battery synthesis sintering energy consumption there is positive meaning.
In sum, the spherical Lithii carbonate that the present invention is prepared can substitute currently marketed micropowder LITHIUM BATTERY carbonic acid
Lithium, and as the spherical Lithii carbonate of the present invention has more preferable mobility relative to micropowder lithium carbonate, therefore to improving powder body
Reunite, the aspect that extends the shelf life has positive effect, also there is positive meaning to reducing battery synthesis sintering energy consumption.This
Outward, the equipment of the microreactor in the face of flourishing, is effectively reduced or eliminates the generation of plugging phenomenon using spherical Lithii carbonate,
Have a good application prospect.
The invention is not limited in aforesaid specific embodiment.The present invention is expanded to and any is disclosed in this manual
New feature or any new combination, and the arbitrary new method that discloses or the step of process or any new combination.