WO2023056676A1 - 一种低温均质制备粒径分布均匀碳酸锂的方法 - Google Patents

一种低温均质制备粒径分布均匀碳酸锂的方法 Download PDF

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WO2023056676A1
WO2023056676A1 PCT/CN2021/128177 CN2021128177W WO2023056676A1 WO 2023056676 A1 WO2023056676 A1 WO 2023056676A1 CN 2021128177 W CN2021128177 W CN 2021128177W WO 2023056676 A1 WO2023056676 A1 WO 2023056676A1
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particle size
lithium
lithium carbonate
size distribution
uniform particle
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French (fr)
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刘志启
刘丽芳
李娜
周自圆
赵鹏程
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安徽大学绿色产业创新研究院
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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

Definitions

  • the invention relates to the field of preparation methods of lithium carbonate, in particular to a method for homogeneously preparing lithium carbonate with uniform particle size distribution at low temperature.
  • the lithium carbonate product particles synthesized by common jacketed heating reactor mixing reaction method are easy to agglomerate and have a wide size distribution. It will cause uneven sintering with other metal oxides, which will eventually affect the electrochemical performance of electrode materials.
  • Lithium carbonate products synthesized by ordinary methods generally have a particle size between 150 and 250 microns, so they generally need to be crushed by physical methods.
  • the commonly used methods in research and application include ultrasonic treatment, high-energy ball milling method, jet milling method, and supergravity reaction method. Even with some control over the course of the reaction.
  • the particle size is also difficult to reach below 50 microns.
  • Some special methods should be used to prepare lithium carbonate fine powder with finer particle size, such as adding electrolyte additives to change its particle size. decrease, affecting its performance.
  • Chinese patent CN202110080435.1 discloses a method for preparing lithium carbonate based on the combination of salt lake ore, lithium polymer and spodumene. Inject carbon dioxide gas with a pressure of 0.5MPa for carbonization reaction, keep the gauge pressure in the carbonization kettle at 0.06-0.08Mpa, and keep the temperature at 48-52°C. After the reaction is completed, wait for the pressure to stabilize, stop feeding carbon dioxide, and open the carbonization kettle to vent The valve exhausts the excess carbon dioxide to obtain a carbonization reaction liquid; the obtained carbonization reaction liquid is centrifuged to obtain solid lithium carbonate.
  • the invention has many whole operation processes and complicated reaction, and also needs a carbonization kettle to carry out the carbonization reaction, and the cost is high.
  • Chinese patent CN20201146856.4 discloses a method for nanoscale lithium carbonate.
  • the method is to freeze a saturated solution or diluent of lithium carbonate at a freezing temperature of -80 to -20°C and a freeze-drying time of 3 to 48 hours. In this method, the temperature is lower during the reaction, and the reaction time is longer. Although the process is simple, the production cost is high.
  • Chinese patent 202010215858.5 discloses a preparation method of lithium carbonate. The method is to add lithium chloride to absolute ethanol to prepare a solution, add sodium hydroxide to absolute ethanol to prepare a solution, and then add lithium chloride alcohol solution to In lithium hydroxide alcohol solution, pass into carbon dioxide gas again, generate lithium carbonate product. This method requires more raw materials, adopts gas-liquid reaction, and has a relatively complicated process, which increases production costs.
  • the purpose of the present invention is to provide a method for preparing lithium carbonate with uniform particle size distribution at low temperature and homogeneously, so as to solve the problems of complicated process and high cost in the preparation method of lithium carbonate products in the prior art.
  • a method for homogeneously preparing lithium carbonate with uniform particle size distribution at low temperature is as follows:
  • Step 1 taking sodium carbonate solution and lithium-containing solution as raw materials
  • Step 2 at first the sodium carbonate solution taken in step 1 is placed in the homogeneous reactor, then the lithium-containing solution used in step 1 is passed into the homogeneous reactor at a constant speed, and the homogeneous reactor is stirred at a constant speed, Sodium carbonate solution and lithium-containing solution are completely reacted in the homogeneous reactor;
  • step 3 After the reaction of step 3 and step 2 is completed, the homogeneous reactor is aged for a period of time;
  • step 4 and step 3 suction filter the interior of the homogeneous reactor to obtain a filter cake, wash and dry the filter cake to obtain a lithium carbonate product with uniform particle size distribution.
  • step 1 the concentration of the sodium carbonate solution taken is 200g/L ⁇ 300g/L, and the temperature of the sodium carbonate solution taken is normal temperature.
  • the concentration of the lithium-containing solution is 15g/L-30g/L
  • the lithium-containing solution is a purified solution or concentrated solution of salt lake brine, or a purified solution or concentrated solution of solid lithium ore, or prepared by lithium chloride solution, or lithium sulfate preparation solution.
  • step 1 the solute mass ratio of the lithium-containing solution to the sodium carbonate solution is 1:1-1:5.
  • step 2 the lithium-containing solution is passed into the internal stator of the homogeneous reactor.
  • step 2 the uniform stirring speed of the homogeneous reactor is 2000-6000 rpm.
  • step 2 after the addition of the lithium-containing solution is completed, the reaction is continued for 10 min to 30 min, so as to achieve the effect of complete reaction.
  • step 3 the aging time is 0.5h-8h.
  • step 4 the filter cake is washed with washing water at a temperature of 80° C. to 100° C., and the number of washings is 1 to 3 times.
  • step 4 the drying temperature is 60°C-105°C, and the drying time is 5h-12h.
  • the present invention uses a lithium-containing solution and a sodium carbonate solution as raw materials and reacts in a homogeneous reactor under low temperature conditions to generate lithium carbonate products.
  • the invention adopts a homogeneous reactor to carry out the whole experimental operation, and utilizes the mechanical shearing force generated between the high-speed rotor and the stator of the homogeneous reactor to reduce the size of solid particles in the mixture.
  • a high shear rate it has a higher circulation rate and accelerates the dispersion of materials.
  • a strong tearing effect is produced on the material, and the size of the droplet is rapidly reduced to a very fine level.
  • the lithium carbonate product can be produced at normal temperature by combining the instrument with the raw materials and method process adopted in the present invention.
  • the present invention has simple technological process, low cost, no heating in the whole process, high preparation efficiency and easy availability of required raw materials.
  • the prepared lithium carbonate is lithium carbonate with uniform particle size distribution and high purity, and the particle size of lithium carbonate is controllable, and the dispersibility is good.
  • lamellar lithium carbonate with regular shape can be obtained without adding any additives.
  • the method of the present invention obviously has better operability, and has more obvious advantages over the lithium carbonate with small particle size prepared by conventional ultrasonic treatment, high-energy ball milling, jet milling, supergravity reaction method and the like.
  • Fig. 1 is a working state diagram of a homogeneous reactor in the present invention.
  • Figure 2 is a particle size distribution diagram of lithium carbonate with uniform particle size distribution in Examples 1 to 5 of the present invention.
  • Fig. 3 is the XRD diagram of the lithium carbonate with uniform particle size distribution of Examples 1 to 5 of the present invention.
  • Fig. 4 is the SEM figure of the lithium carbonate with uniform particle size distribution of Examples 1 to 5 of the present invention.
  • the present invention is based on problems such as relatively serious agglomeration phenomenon of lithium carbonate product in the prior art, shape is difficult to control, particle size is larger and unevenly distributed, provides a kind of brand-new preparation method of lithium carbonate with uniform particle size distribution, the preparation The method is simple in operation, low in cost, and can obtain a lithium carbonate product with small particle size, uniform distribution, good dispersibility and good shape without heating during the reaction.
  • the rotor speed of the device is 2000rpm to realize the stirring reaction, wherein the solute mass ratio of the lithium-containing solution to the sodium carbonate solution is 1:1.5, no heating is required during the reaction process, and the reaction is continued for 10 minutes after the introduction of the lithium-containing solution is completed.
  • the homogeneous reactor was allowed to age for 2 hours, and then the product in the homogeneous reactor was separated by suction filtration (realized by a solid-liquid separator) to obtain a filter cake, and then the filter cake was washed with 80°C hot water for 3 times, and the The filter cake was dried at 105°C to obtain lithium carbonate product.
  • the particle size distribution diagram of the lithium carbonate product is shown in Figure 2, the XRD diagram is shown in Figure 3, and the scanning electron microscope diagram is shown in Figure 4.
  • the yield of the prepared lithium carbonate product was 83.62%, and the median diameter D50 of the particle size was 29.78 ⁇ m.
  • the test results of the laser particle size distribution analyzer are shown in Table 1.
  • Table 1 is the particle size test result of embodiment 1 lithium carbonate
  • the homogeneous reactor was allowed to age for 2 hours, and then the product in the homogeneous reactor was separated by suction filtration to obtain a filter cake, and the filter cake was washed with hot water at 80°C for 3 times, and then dried at 105°C dry to obtain lithium carbonate product.
  • the particle size distribution figure of lithium carbonate product is as shown in Figure 2, the XRD figure is as shown in Figure 3, and the scanning electron microscope figure is as shown in Figure 4b, and the productive rate of preparing lithium carbonate product is 84.33%, and the median diameter D50 of particle size is 12.70 ⁇ m, the test results of the laser particle size distribution analyzer are shown in Table 2.
  • Table 2 is the particle size test result of embodiment 2 lithium carbonate
  • the particle size range of lithium carbonate is 2.023 to 51.97 ⁇ m, the particle size is significantly smaller than that of the product in Example 1, and the particle size distribution is also significantly narrowed.
  • Fig. 3 there is only one pure phase of lithium carbonate, and there is no obvious impurity peak, indicating that the purity of the lithium carbonate product is higher.
  • the characteristic diffraction peak intensity is high and the peak shape is sharp, indicating that the product has a strong structural regularity.
  • From b) in Figure 4 it can be seen that lithium carbonate crystals have good dispersion, relatively uniform morphology, and narrow particle size distribution.
  • the homogeneous reactor was allowed to age for 2 hours, and then the product in the homogeneous reactor was separated by suction filtration to obtain a filter cake, and the filter cake was washed with hot water at 80°C for 3 times, and then dried at 105°C dry to obtain lithium carbonate product.
  • the particle size distribution figure of lithium carbonate product is as shown in Figure 2, the XRD figure is as shown in Figure 3, and the scanning electron microscope figure is as shown in Figure 4c, and the productive rate of preparing lithium carbonate product is 87.14%, and the median diameter D50 of particle size is 9.614 ⁇ m, the test results of the laser particle size distribution analyzer are shown in Table 3.
  • Table 3 is the particle size test result of embodiment 3 lithium carbonate
  • the particle size of lithium carbonate ranges from 1.881 to 30.21 ⁇ m. It can be seen from Figure 3 that there is only one pure phase of lithium carbonate, and no obvious impurity peaks indicate that the lithium carbonate product has a high purity. The characteristic diffraction peak intensity is high and the peak shape is sharp, indicating that the product has a strong structural regularity. From c) in Fig. 4, it can be seen that the dispersibility of lithium carbonate crystals is better, the morphology is more uniform, and the particle size distribution is narrow.
  • the homogeneous reactor was allowed to age for 2 hours, and then the product in the homogeneous reactor was separated by suction filtration to obtain a filter cake, and then the filter cake was washed with 80°C hot water for 3 times, and the filter cake was dried at 105°C , to obtain lithium carbonate product.
  • the particle size distribution figure of Lithium Retard product is as shown in Figure 2, the XRD figure is as shown in Figure 3, and the scanning electron microscope figure is as shown in Figure 4, the productive rate of preparing Lithium Retard product is 89.67%, and the median diameter D50 of particle diameter is 8.501 ⁇ m, the test results of the laser particle size distribution analyzer are shown in Table 4.
  • Table 4 is the particle size test result of embodiment 4 lithium carbonate
  • the particle size distribution figure of lithium carbonate product is as shown in Figure 2, and the XRD figure is as shown in Figure 3, and the productive rate of preparing lithium carbonate product is 87.47%, and the median diameter D50 of particle size is 10.75 ⁇ m, laser particle size distribution analyzer test result As shown in Table 5.
  • Table 5 is the particle size test result of embodiment 5 lithium carbonate
  • the particle size range of lithium carbonate is 2.054-26.00 ⁇ m. It can be seen from Figure 2 that the peak shape of the lithium carbonate product is relatively sharp, indicating that the particle size distribution of the product is narrow and the uniformity is good. As can be seen from Figure 3, there is only one pure phase of lithium carbonate, and there is no obvious impurity peak, indicating that the product has a higher purity.

Abstract

一种低温均质制备粒径分布均匀碳酸锂的方法，以含锂溶液为原料，低温条件下，将该含锂溶液加入碳酸钠溶液中，于均质反应器中进行反应，待反应结束后陈化静置，过滤洗涤，经干燥即可得粒径均匀的碳酸锂。采用均质乳化法，于低温条件下反应，得到粒径分布均匀的碳酸锂。该方法操作简单，耗能低，反应效率高，且所得碳酸锂粒径、形貌可控，分散性高，反应过程中无需添加助剂即可得到形貌规整的碳酸锂，可大规模应用于工业化生产碳酸锂。

Description

一种低温均质制备粒径分布均匀碳酸锂的方法 技术领域
本发明涉及碳酸锂制备方法领域，具体是一种低温均质制备粒径分布均匀碳酸锂的方法。
背景技术
目前应用最为广泛的是便携式电子设备，动力电池等一些高科技应用领域对碳酸锂产品质量提出了更高的要求，除了对碳酸锂纯度有严格的要求，对碳酸锂颗粒和形貌也有很高的要求，不同尺度的颗粒分离工艺对于固体加工技术中微纳米材料的生产具有重要意义。
碳酸锂制备过程中一般采用普通的夹套式加热反应器混合反应的方法合成的的碳酸锂产品颗粒之间易团聚，尺度分布广。会造成与其他金属氧化物混合烧结不均匀现象，最终影响电极材料的电化学性能。普通方法合成的碳酸锂产品一般粒度在150～250微米之间，因此一般情况下都需要通过物理办法进行破碎。目前，研究应用中常用的方法有超声波处理、高能球磨发法、气流粉碎法、超重力反应法等。即使在反应过程中采用一些控制手段。粒度也很难达到50微米以下，制备粒度更细的碳酸锂微粉应采用一些特殊的办法，例如添加电解质添加剂改变其粒径，但在这过程中难免经常性的引入其他的杂质离子，导致纯度降低，影响其性能。
中国专利CN202110080435.1公开了一种基于盐湖矿石、锂聚合物以及锂辉石组合的碳酸锂制备方法，该方法采用氢氧化锂料浆为原料，经离心分离、溶解,再进入碳化釜，通入压力为0.5MPa的二氧化碳气体进行碳化反应，保持碳化釜内的表压在0.06～0.08Mpa，保持温度在48～52℃，反应完成后待压力稳定，停止通入二氧化碳，并开启碳化釜放空阀将过量二氧化碳排空，得到碳化反应液；将所得的碳化反应液经离心分离后,得到固体碳酸锂。该发明整个操作流程多，反应复杂，还需要碳化釜进行碳化反应，成本高。中国专利CN20201146856.4公开了一种纳米级碳酸锂的方法，该方法是将碳酸锂饱和溶液或稀释液进行冷冻，冷冻温度为-80～-20℃，冷冻干燥时间为3～48小时。该方法在反应过程中温 度较低，反应时间较长，虽工艺简单，但生产成本高。中国专利202010215858.5公开了一种碳酸锂的制备方法，该方法是将氯化锂加入无水乙醇中配制成溶液，将氢氧化钠加入无水乙醇中配制成溶液，然后将氯化锂醇溶液加入氢氧化锂醇溶液中，再通入二氧化碳气体，生成碳酸锂产品。该方法所需原料较多，采用气液反应，工艺较为复杂，增加生产成本。
发明内容
本发明的目的是提供一种低温均质制备粒径分布均匀碳酸锂的方法，以解决现有技术碳酸锂产品制备方法工艺繁琐、成本高的问题。
为了达到上述目的，本发明所采用的技术方案为：
一种低温均质制备粒径分布均匀碳酸锂的方法，过程如下：
步骤1、取用碳酸钠溶液和含锂溶液为原料；
步骤2、首先将步骤1取用的碳酸钠溶液置于均质反应器内，然后向均质反应器内匀速通入步骤1取用的含锂溶液，并令均质反应器内匀速搅拌，使碳酸钠溶液与含锂溶液在均质反应器内完全反应；
步骤3、步骤2反应结束后，令均质反应器陈化一段时间；
步骤4、步骤3陈化后，对匀质反应器内部抽滤得到滤饼，将滤饼洗涤后干燥，得到粒径分布均匀的碳酸锂产品。
进一步的，步骤1中，取用的碳酸钠溶液的浓度为200g/L～300g/L，取用的碳酸钠溶液的温度为常温。
进一步的，步骤1中，含锂溶液的浓度为15g/L～30g/L，含锂溶液为盐湖卤水的净化液或浓缩液、或者固体锂矿的净化液或浓缩液、或者氯化锂配制液、或者硫酸锂配制液。
进一步的，步骤1中，含锂溶液与碳酸钠溶液的溶质质量比为1:1～1:5。
进一步的，步骤2中，含锂溶液通入至均质反应器内部定子处。
进一步的，步骤2中，均质反应器的匀速搅拌速度为2000～6000rpm。
进一步的，步骤2中，待含锂溶液加入完毕后，继续反应10min～30min，以达到反应完全的效果。
进一步的，步骤3中，陈化时间为0.5h～8h。
进一步的，步骤4中，采用温度为80℃～100℃的洗涤水对滤饼进行洗涤， 洗涤次数为1～3次。
进一步的，步骤4中，干燥温度为60℃～105℃，干燥时间为5h～12h。
针对现有技术存在的问题，本发明以含锂溶液和碳酸钠溶液为原料、在低温的条件下，以均质反应器进行反应，即可生成碳酸锂产品。
本发明采用均质反应器进行整个实验操作，利用均质反应器高速转子和定子间产生机械剪切力，能够减小混合物中固体颗粒尺寸。在高剪切速率下，具有较高的循环量，加速物料分散。在高速剪切作用下，对物料产生强烈的撕裂作用，液滴的尺寸迅速降到非常细的程度。通过该仪器结合本发明所采用的原料和方法过程，常温下就能够制得碳酸锂产品。
因此，本发明工艺流程简单，成本低，整个过程无须加热，制备效率高，所需的原料易得。制备出的碳酸锂为粒径大小分布均匀、纯度高的碳酸锂，并且碳酸锂颗粒大小可控，分散性好，反应过程中无需加入任何添加剂就可制得形貌规整的片层状碳酸锂。本发明方法相比现有技术，明显具有更好的可操作性，相对于常用的超声波处理、高能球磨、气流粉碎、超重力反应法等制备的小粒径的碳酸锂具有更明显的优势。
附图说明
图1是本发明中均质反应器工作状态图。
图2是本发明实施例1～实施例5的粒径分布均匀的碳酸锂的粒径分布图。
图3是本发明实施例1～实施例5的粒径分布均匀的碳酸锂的XRD图。
图4是本发明实施例1～实施例5的粒径分布均匀的碳酸锂的SEM图。
具体实施方式
以下具体说明本发明的的进一步实施方式，该详细说明不应该认为是本发明的限制，而应理解为是对本发明的某些方面,特性和实施方案的更详细的描述。
本发明基于现有的技术中碳酸锂产品团聚现象比较严重，形貌难以控制，粒径较大且分布不均匀等问题，提供一种全新的粒径分布均匀的碳酸锂的制备方法，该制备方法操作简单，成本低，反应时无需加热即可获得粒径较小且分布均匀，分散性好，形貌较好的碳酸锂产品。
本发明所采用的均质反应器其工作状态如图1所示，通过一路带阀门的第一管路3.1先将碳酸钠溶液加入至均质反应器1内部，然后通过带阀门的第二管路 3.2将含锂溶液匀速通入至均质反应器1的定子2所在位置，反应结束后均质反应器1的产物通过输出管输出至固液分离器4进行固液分离，最终得到碳酸锂产品。
实施例1
常温下，取浓度为200g/L碳酸钠溶液先置于均质反应器中，然后向均质反应器的定子位置匀速通入浓度为15g/L的盐湖卤水含锂溶液，并令均质反应器的转子转速为2000rpm实现搅拌反应，其中含锂溶液与碳酸钠溶液的溶质质量比为1:1.5，反应过程无需加热，待含锂溶液通入完成，继续反应10min。反应结束后，令均质反应器陈化2h，然后抽滤分离均质反应器内产物(通过固液分离器实现)得到滤饼，再采用80℃的热水洗涤滤饼3次后，将滤饼于105℃条件下烘干，得到碳酸锂产品。
碳酸锂产品的粒度分布图如2所示，XRD图如图3所示，电镜扫描图如图4所示。制备出碳酸锂产品的产率为83.62％，粒径的中位径D50为29.78μm，激光粒度分布仪测试结果如表1所示。
表1 为实施例1碳酸锂的粒径测试结果
D03＝2.632μm D06＝5.268μm D10＝9.398μm D16＝13.56μm D25＝18.00μm
D75＝45.13μm D50＝29.78μm D84＝52.29μm D90＝58.42μm D97＝71.01μm
从表1可以看出D03＝2.632μm，D97＝71.01μm。说明实施例1所制备的碳酸锂产品粒度较大，粒径分布较广。从图3可以看出，只存在碳酸锂一个纯相，无明显杂质峰，说明该碳酸锂产品纯度较高。特征衍射峰强度高，峰型尖锐，说明产品结构规整性强。从图4a可以看出碳酸锂晶体分散性较好，形貌比较均一，但颗粒还是偏大，粒径分布较广。
实施例2
常温下，取浓度为300g/L碳酸钠溶液先置于均质反应器中，然后向均质反应器的定子位置匀速通入浓度为30g/L的固体锂矿浓缩液含锂溶液，并令均质反应器的转子转速为3000rpm实现搅拌反应，其中含锂溶液与碳酸钠溶液的溶质质量比为1:1.2，反应过程无需加热，待含锂溶液通入完成，继续反应10min。反应结束后，令均质反应器陈化2h，然后抽滤分离均质反应器内产物得到滤饼，再采用80℃的热水洗涤滤饼3次后，将滤饼于105℃条件下烘干，得到碳酸锂产 品。
碳酸锂产品的粒度分布图如图2所示，XRD图如图3所示，电镜扫描图如图4b所示，制备出碳酸锂产品的产率为84.33％，粒径的中位径D50为12.70μm，激光粒度分布仪测试结果如表2所示。
表2 为实施例2碳酸锂的粒径测试结果
D03＝2.023μm D06＝2.722μm D10＝3.438μm D16＝4.443μm D25＝6.093μm
D75＝25.38μm D50＝12.70μm D84＝32.59μm D90＝38.99μm D97＝51.97μm
从表2可以看出碳酸锂的粒径范围为2.023～51.97μm，粒度较实例1产品粒度明显变小，粒径分布也明显变窄。从图3可以看出只存在碳酸锂一个纯相，无明显杂质峰,说明该碳酸锂产品纯度较高。特征衍射峰强度高，峰型尖锐，说明产品结构规整性强。从图4中的b)可以看出碳酸锂晶体分散性较好，形貌比较均一，粒径分布较窄。
实施例3
常温下，取浓度为200g/L碳酸钠溶液先置于均质反应器中，然后向均质反应器的定子位置匀速通入浓度为30g/L的固体锂矿净化液，并令均质反应器的转子转速为4000rpm实现搅拌反应，其中含锂溶液与碳酸钠溶液的溶质质量比为1:5，反应过程无需加热，待含锂溶液通入完成，继续反应10min。反应结束后，令均质反应器陈化2h，然后抽滤分离均质反应器内产物得到滤饼，再采用80℃的热水洗涤滤饼3次后，将滤饼于105℃条件下烘干，得到碳酸锂产品。
碳酸锂产品的粒度分布图如图2所示，XRD图如图3所示，电镜扫描图如图4c所示，制备出碳酸锂产品的产率为87.14％，粒径的中位径D50为9.614μm，激光粒度分布仪测试结果如表3所示。
表3 为实施例3碳酸锂的粒径测试结果
D03＝1.881μm D06＝2.612μm D10＝3.307μm D16＝4.215μm D25＝5.556μm
D75＝15.77μm D50＝9.614μm D84＝19.40μm D90＝22.91μm D97＝30.12μm
从表3可以看出碳酸锂的粒径范围为1.881～30.21μm，从图3可以看出只存在碳酸锂一个纯相，无明显杂质峰说明该碳酸锂产品纯度较高。特征衍射峰强度高，峰型尖锐，说明产品结构规整性强。从图4中的c)可以看出碳酸锂晶体分 散性较好，形貌比较均一,粒径分布窄。
实施例4
常温下，取浓度为200g/L碳酸钠溶液先置于均质反应器中，然后向均质反应器的定子位置匀速通入浓度为30g/L的固体锂矿净化液含锂溶液，并令均质反应器的转子转速为5000rpm实现搅拌反应，其中含锂溶液与碳酸钠溶液的溶质质量比为1:5，反应过程无需加热，待含锂溶液通入完成，继续反应10min。反应结束后，令均质反应器陈化2h，然后抽滤分离均质反应器内产物得到滤饼，再采用80℃的热水洗涤滤饼3次，将滤饼于105℃条件下烘干，得到碳酸锂产品。
碳酸锂产品的粒度分布图如图2所示，XRD图如图3所示，电镜扫描图如图4所示，制备出碳酸锂产品的产率为89.67％，粒径的中位径D50为8.501μm，激光粒度分布仪测试结果如表4所示。
表4 为实施例4碳酸锂的粒径测试结果
D03＝1.754μm D06＝2.457μm D10＝3.106μm D16＝3.911μm D25＝5.065μm
D75＝13.31μm D50＝8.501μm D84＝16.20μm D90＝18.91μm D97＝25.06μm
从表4可以看出碳酸锂的粒径范围为1.754～25.06μm，粒度较以上产品粒度明显变小，粒径分布也更窄。从图3可以看出只存在碳酸锂一个纯相，无明显杂质峰。从图4中的d)可以看出碳酸锂晶体分散性较好，形貌比较均一，规整性好，粒径分布窄。
实施例5
常温下，取浓度为200g/L碳酸钠溶液先置于反应器中，然后向均质反应器的定子位置匀速通入浓度为30g/L的固体锂矿净化液含锂溶液，并令均质反应器的转子转速为6000rpm实现搅拌反应，其中含锂溶液与碳酸钠溶液的溶质质量比为1:5，反应过程无需加热，待含锂溶液通入完成，继续反应10min。反应结束后，令均质反应器陈化2h，然后抽滤分离均质反应器内产物得到滤饼，再采用80℃的热水洗涤滤饼3次，将滤饼于105℃条件下烘干，得到碳酸锂产品。
碳酸锂产品的粒度分布图如图2所示，XRD图如图3所示，制备出碳酸锂产品的产率为87.47％，粒径的中位径D50为10.75μm，激光粒度分布仪测试结果如表5所示。
表5 为实施例5碳酸锂的粒径测试结果
D03＝2.054μm D06＝2.933μm D10＝3.822μm D16＝5.045μm D25＝6.716μm
D75＝15.55μm D50＝10.75μm D84＝18.09μm D90＝20.51μm D97＝26.00μm
从表5可以看出碳酸锂的粒径范围为2.054～26.00μm，从图2可看出该碳酸锂产品峰型较尖锐，说明产品粒径分布窄，均一性很好。从图3可以看出只存在碳酸锂一个纯相，无明显杂质峰，说明产品纯度较高。
本发明所述的实施例仅仅是对本发明的优选实施方式进行的描述，并非对本发明构思和范围进行限定，在不脱离本发明设计思想的前提下，本领域中工程技术人员对本发明的技术方案作出的各种变型和改进，均应落入本发明的保护范围，本发明请求保护的技术内容，已经全部记载在权利要求书中。

Claims (10)

  1. 一种低温均质制备粒径分布均匀碳酸锂的方法，其特征在于，过程如下：
    步骤1、取用碳酸钠溶液和含锂溶液为原料；
    步骤2、首先将步骤1取用的碳酸钠溶液置于均质反应器内，然后向均质反应器内匀速通入步骤1取用的含锂溶液，并令均质反应器匀速搅拌，使碳酸钠溶液与含锂溶液在均质反应器内完全反应；
    步骤3、步骤2反应结束后，令均质反应器陈化一段时间；
    步骤4、步骤3陈化后，对匀质反应器内部抽滤得到滤饼，将滤饼洗涤后干燥，得到粒径分布均匀的碳酸锂产品。
  2. 根据权利要求1所述的一种低温均质制备粒径分布均匀碳酸锂的方法，其特征在于，步骤1中，取用的碳酸钠溶液的浓度为200g/L～300g/L，取用的碳酸钠溶液的温度为常温。
  3. 根据权利要求1所述的一种低温均质制备粒径分布均匀碳酸锂的方法，其特征在于，步骤1中，含锂溶液的浓度为15g/L～30g/L，含锂溶液为盐湖卤水的净化液或浓缩液、或者固体锂矿的净化液或浓缩液、或者氯化锂配制液、或者硫酸锂配制液。
  4. 根据权利要求1所述的一种低温均质制备粒径分布均匀碳酸锂的方法，其特征在于，步骤1中，含锂溶液与碳酸钠溶液的溶质质量比为1:1～1:5。
  5. 根据权利要求1所述的一种低温均质制备粒径分布均匀碳酸锂的方法，其特征在于，步骤2中，含锂溶液通入至均质反应器内部定子处。
  6. 根据权利要求1所述的一种低温均质制备粒径分布均匀碳酸锂的方法，其特征在于，步骤2中，均质反应器的匀速搅拌速度为2000～6000rpm。
  7. 根据权利要求1所述的一种低温均质制备粒径分布均匀碳酸锂的方法，其特征在于，步骤2中，待含锂溶液加入完毕后，继续反应10min～30min，以达到反应完全的效果。
  8. 根据权利要求1所述的一种低温均质制备粒径分布均匀碳酸锂的方法，其特征在于，步骤3中，陈化时间为0.5h～8h。
  9. 根据权利要求1所述的一种低温均质制备粒径分布均匀碳酸锂的方法， 其特征在于，步骤4中，采用温度为80℃～100℃的洗涤水对滤饼进行洗涤，洗涤次数为1～3次。
  10. 根据权利要求1所述的一种低温均质制备粒径分布均匀碳酸锂的方法，其特征在于，步骤4中，干燥温度为60℃～105℃，干燥时间为5h～12h。
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