• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    The present invention relates to a green and low-cost ternary material precursor, and a preparation method and device thereof, and pertains to the field of 5 new energy power batteries. Nickel salt, manganese salt and cobalt salt are mixed to obtain a mixed salt solution of a certain concentration, and are sent, together with an environment-friendly complexing agent of a certain concentration and a precipitator, into a reaction tank filled with N2 for protection, and reaction conditions are strictly controlled, wherein a feeding speed of the precipitator is controlled by a pH automatic 10 charging machine; the product obtained is pumped into a circulation tank from the bottom of the reaction tank, and enters the reaction tank again through an overflow port after the circulation tank is full of reaction liquid, and the circulation will be repeated like this for many times; the reaction will be immediately stopped when the particle size of the precursor meets the requirement; and a ternary precursor material 15 will be obtained after filtering, washing and drying. The technology adopted in the present invention overcomes the defect of comparatively wide particle size distribution of traditional technologies. The precursor prepared according to the present invention has qualified content of all metals, reasonable particle size distribution and high sphericity; and the technology is simple, green, low-cost and applicable for industrial 20 promotion. Figure 1
    公开号:NL2026949A
    申请号:NL2026949
    申请日:2020-11-21
    公开日:2021-02-02
    发明作者:Qin Xianzhong；Cai Feipeng；Jiang Bo；Jiang Guilin
    申请人:Energy Res Inst Shandong Academy Sciences；
    IPC主号:
    专利说明:

    GREEN AND LOW-COST TERNARY MATERIAL PRECURSOR, ANDPREPARATION METHOD AND DEVICE THEREOF
    TECHNICAL FIELD The present invention relates to a ternary material precursor of lithium-ion batteries, and a preparation method and device thereof, and pertains to the field of new energy power battery. Specifically, the present invention relates to a preparation method of a green and low-cost ternary material precursor.
    BACKGROUND ART At present, power batteries with a ternary material (LiNixCoyMn1-x-yQ2), particularly a high-nickel ternary material (LiNixCoyMn1-x-yO2, x>0.6), as the positive electrode have been preferred by many domestic battery enterprises. Based on a proportion of the three elements, i.e. Ni:Co:Mn, the LiNixCoyMn1-x-yO2 material can be classified as 111, 523, 622 and 811 types or the like, wherein Ni, as a principal active element, can enhance the specific capacity, Co can improve the conductivity, and Mn can stabilize the material structure, so the increase of Ni content can enhance the material capacity, but will also lower rate capability, cycle life and security.
    Currently, ternary materials are mainly prepared through the high-temperature solid- phase reaction of a hydroxide precursor and a lithium salt, the hydroxide precursor material being basically obtained by using a co-precipitation technology, and its leading indicators include content of three elements Ni, Co and Mn, total metal content, tap density, particle size distribution, specific surface area, morphology and so on. The content of the three elements is an important indicator for judging whether the precursor material is qualified, the total metal content is a key indicator for blending lithium, and the tap density, the particle size distribution, the specific surface area, the morphology and so on will influence the later high-temperature sintering technology and the performance of finished products. The element composition, grain morphology, particle size distribution, tap density or the like of the precursor material are decisive for the physical and electrochemical properties of the final products. For the time being, precursors are prepared by using continuous co-precipitation and intermittent co-precipitation, wherein the continuous co-precipitation is a continuous production realized in a reaction kettle with an overflow port, in which feeding and discharging of material are executed simultaneously, but the disadvantage is that the particle size distribution of the obtained precursor is comparatively wide; while the intermittent co- precipitation is to carry out multiple precipitations intermittently in an airtight reaction kettle, and the advantage is that the obtained precursor material is of high quality and has a uniform particle size. It is discovered by the inventors that the latest preparation method of ternary precursors can overcome the problem of comparatively wide particle size of the traditional continuous co-precipitation, but the operation is complicated, and some other matching apparatuses are needed, such as an aging pool, an off-shooter, a concentrator and so on; ammonium hydroxide, used as a complexing agent in the process of synthesis, will lead to the release of NH3 and a large amount of alkaline supernatant, thereby causing environmental pollution and cost increase for dealing with the waste fluid; moreover, the content of the three elements in the precursor material is not studied.
    SUMMARY OF THE INVENTION In order to overcome the above problem, the present invention provides a green and low-cost ternary material precursor, and a preparation method and device thereof. The ternary material precursor prepared according to the present invention has the advantages of qualified content of all metals, primary particles having an appropriate size and being stacked densely, and secondary particles having reasonable particle size distribution, a high sphericity and tap density; besides, the technology is simple, green and low energy-consuming, and is suitable for industrial promotion.
    To accomplish the aforementioned technical object, the following technical solution is adopted in the present invention.
    According to a first aspect of the present invention, there is provided a preparation method of a green and low-cost ternary material precursor, comprising the steps of: performing intermittent co-precipitation with a mixed solution containing nickel salt, manganese salt and cobalt salt, an environment-friendly complexing agent, and a precipitator as raw materials, and collecting product; returning the product to the intermittent co-precipitation process for a seed crystal circulation; and taking out mother liquid and overflow product after reaction, and obtaining a ternary material precursor after filtering, washing and drying.
    The present invention adopts the intermittent co-precipitation+seed crystal circulation technology to overcome the defect of comparatively wide particle size distribution of the precursor prepared through the traditional continuous co- precipitation technology; environment-friendly complexing agent is adopted in the synthesis process, thereby avoiding the release of NH3 and a large amount of alkaline supernatant during the reaction with regular ammonium hydroxide as the complexing agent, which causes environmental pollution and cost increase for dealing with the waste fluid; instead of adjusting and controlling pH value through constant manual addition of acid or alkali for a long time, a pH automatic charging machine is used for controlling a feeding speed of the precipitator so as to rapidly maintain pH stabilization during the reaction; moreover, the produced supernatant can also be used as a heat treating atmosphere for dealing with CO2 in the air.
    According to a second aspect of the present invention, there is provided a ternary material precursor prepared by using any of the above methods, wherein the ternary material precursor is one of NixCoyMn1-x-yCO3 and NixCoyMn1-x-y (OH)2 (O<x<1, O<y<1), or a mixture thereof.
    The ternary material precursor prepared according to the present invention has the advantages of qualified content of all metals, primary particles having an appropriate size and being stacked densely, and secondary particles having reasonable particle size distribution, a high sphericity and tap density; meanwhile, lithium batteries produced with this ternary material precursor as the raw material are also obviously superior to those prepared by using existing methods in discharging specific capacity and circulation retention ratio.
    According to a third aspect of the present invention, there is provided a preparation device of a green and low-cost ternary material precursor, comprising: a reaction tank and a circulation tank, wherein a fluid discharging pipe at the bottom of the reaction tank is connected with a fluid charging pipe at the bottom of the circulation tank, an overflow pipe provided at an upper part of the circulation tank is connected with an inlet provided at an upper part of the reaction tank, and the reaction tank and the circulation tank are connected with a plurality of filling devices and gas charging devices, respectively.
    Based on the intermittent co-precipitation+seed crystal circulation technology of the present invention, the present invention designs a corresponding production device with a simple structure, and the device is convenient, practical and can be easily promoted.
    The beneficial effects of the present invention are as follows.
    (1) The present invention adopts the intermittent co-precipitation+seed crystal circulation technology so as to overcome the defect of comparatively wide particle size distribution of the precursor prepared through the traditional continuous co-precipitation technology; environment-friendly complexing agent is adopted in the synthesis process, thereby avoiding the release of NH3 and a large amount of alkaline supernatant during the reaction with regular ammonium hydroxide as the complexing agent, which causes environmental pollution and cost increase for dealing with the waste fluid; instead of adjusting and controlling pH value through constant manual addition of acid or alkali for a long time, a pH automatic charging machine is used for controlling a feeding speed of the precipitator so as to rapidly maintain pH stabilization during the reaction; moreover, the produced supernatant can also be used as a heat treating atmosphere for dealing with CO2 in the air; (2) The ternary material precursor prepared according to the present invention has the advantages of qualified content of all metals, primary particles having an appropriate size and being stacked densely, and secondary particles having reasonable particle size distribution, a high sphericity and tap density; meanwhile, lithium batteries produced with this ternary material precursor as the raw material are also obviously superior to those prepared by using existing methods in discharging specific capacity and circulation retention ratio; and (3) The method of the present invention is simple, convenient to carry out, highly practical, and easy to promote.
    DESCRIPTION OF DRAWINGS The drawings below are incorporated into the specification and constitute a part of the specification, and are used for facilitating further understanding of the present invention. Schematic examples of the present invention and explanations of them are used for explaining the present invention, and do not constitute inappropriate limits to the present invention.
    Fig.1 is a schematic diagram of the intermittent co-precipitation+seed crystal circulation reaction in Example 1 of the present invention; and Fig. 2 is a picture of SEM precursors of the products prepared in Example 1 and Contrastive Example 1 of the present invention.EMBODIMENTS
    It should be pointed out that the following detailed description are all exemplary, and are intended to further explain the present invention. Unless otherwise specified, all of the technologies and scientific terms used in the present invention have the same meaning as those commonly understood by an ordinary person skilled 5 inthe technical field to which the present invention pertains.
    It should be noted that the terms used herein are merely for describing the embodiments, and are not intended to limit the exemplary implementation modes according to the present invention. As used herein, unless otherwise specified, the singular form also intends to include the plural form; besides, it should be understood that the terms “comprising” and/or “including” used in the present specification indicate the existence of features, steps, operations, devices, components and/or combinations thereof.
    A preparation method of a green and low-cost ternary material precursor, specifically comprising the steps of: nickel salt, manganese salt and cobalt salt are prepared into a mixed salt solution of a certain concentration according to a certain stoichiometric ratio, and are sent, together with an environment-friendly complexing agent of a certain concentration and a precipitator, into a reaction tank filled with N2 for protection, and concentration, reaction temperature, stirring speed and other fluid mechanical conditions are strictly controlled during the reaction, wherein a feeding speed of precipitator is controlled by a pH automatic charging machine so as to maintain pH stabilization during the reaction; after a period of reaction, the product is pumped into a circulation tank from the bottom of the reaction tank, and enters the reaction tank again through an overflow after the circulation tank is full of reaction liquid, and the circulation will be repeated like this for many times; precursor particle size during reaction is detected by an optical microscope and a laser particle size analyzer, and the reaction will be immediately stopped when the particle size meets the requirement; the reaction tank and overflow product are taken out, and uniform ternary precursor material with controllable particle size distribution will be obtained after filtering, washing and drying.
    In some examples, the precursor is one of NixCoyMn1-x-yCO3 and NixCoyMn1-x-y (OH)2 (O<x<1, O<y<1), or a mixture of them; and the ternary material precursor prepared according to the present invention has the advantages of qualified content of all metals, primary particles having an appropriate size and being stacked densely, and secondary particles having reasonable particle size distribution, a high sphericity and tap density. Meanwhile, lithium batteries produced with this ternary material precursor as the raw material are also obviously superior to those prepared by using existing methods in discharging specific capacity and circulation retention ratio.
    In some examples, the precipitator is one of Na2C03, NaHCO3, (NH4)2C0O3, NH4HCO3, K2CO3, KHCO3, NaOH and KOH, or a mixture of some thereof; and a feeding speed of the precipitator is adjusted by pH automatic controlling so that pH stabilization during the reaction is rapidly maintained without manual controlling, as a result, the ternary material precursor has a fine morphologic structure.
    In some examples, the environment-friendly complexing agent is Amino carboxylic acids, phosphonates, hydroxyl carboxylic acids, amino acids and polycarboxylic acids. The use of the environment-friendly complexing agent can avoid the release of NH3 and a large amount of alkaline supernatant during the reaction with regular ammonium hydroxide as the complexing agent, which causes environmental pollution and cost increase for dealing with the waste fluid.
    The types of nickel salt are not particularly limited in the present application.
    In some examples, the nickel salt is one of Ni(NO3)2, NiClI2, NiSO4, NiC204 and (CH3COO)2Ni, or a mixture of some thereof, so as to form the ternary material precursor with cobalt and manganese.
    The types of cobalt salt are not particularly limited in the present application. In some examples, the cobalt salt is one of Co(NO3)2, CoCl2, CoS04, CoC204 and (CH3CO00)2Co, or a mixture of some thereof, so as to prepare a mixed salt solution of a target concentration.
    The types of manganese salt are not particularly limited in the present application. In some examples, the manganese salt is one of Mn(NO3)2, MnCl2, MnS04, MnC204 and (CH3COO)2Mn, or a mixture of some thereof, so as to prepare the ternary material precursor after co-precipitation and seed crystal circulation.
    In order to make sure that the prepared ternary material precursor has qualified metal content, and fine morphology structure and particle size, it is necessary to optimize the concentration of the salt solution, the precipitator and the complexing agent. As a result, in some examples, the concentration of the mixed salt is 0.1-10 M; the precipitator has a concentration of 0.1-10 mol/L; and the complexing agent has a concentration of 0.1-10 mol/L; and the obtained ternary material precursor has a good morphology structure and a uniform particle size, as well as a high discharging capacity and a high discharging circulation retention ratio.
    In some examples, the fluid mechanic conditions are as follows: the feeding of precipitator is adjusted and controlled by a pH automatic charging machine so that pH is maintained at 8-11, the stirring speed is 300-1000 r/min, the reaction temperature is 30-80°C, the feeding speed is 1-10 ml/min, the reaction time is 0.1-50 hours, and the tank volume is 0.5-100 L. Instead of adjusting and controlling pH value through constant manual addition of acid or alkali for a long time, a pH automatic charging machine is used for controlling a feeding speed of the precipitator so as to rapidly maintain pH stabilization during the reaction.
    With reference to specific examples, the present invention will be further elaborated below. It should be understood that the specific examples are to explain the present invention, rather than limiting the present invention.
    Example 1 Weigh and take a certain amount of Ni(NO3)2, Co(NO3)2 and Mn(NO3)2 according to a Ni:Co:Mn mole ratio of 0.5:0.2:0.3, dissolve them into deionized water to prepare a mixed salt solution having a concentration of 0.1 mol/L, and input the mixed salt solution into a reaction kettle of | L together with a sodium citrate solution having a concentration of 0.1mol/L, wherein the reaction temperature is 30°C, the feeding speed is controlled to be 1 ml/min, the stirring intensity is 300 r/min, and a pH automatic charging machine is used to adjust the precipitator NaOH (0.2mol/L) to have a pH value of 10 during the reaction. After the reaction solution stays in the reaction kettle for 0.5 hours, the product is pumped into the circulation tank together with the reaction solution, and then overflows back into the reaction tank. After 5 hours of stirring and reaction, the final product is filtered, washed and dried to obtain a precursor material Ni0.5C00.2Mn0.3(0OH)2.
    Example 2 Weigh and take a certain amount of NiC204, CoC204 and MnC204 according to a Ni:Co:Mn mole ratio of 0.6:0.2:0.2, dissolve them into deionized water to prepare a mixed salt solution having a concentration of 10 mol/L, and input the mixed salt solution into a reaction kettle together with a polyacrylic acid solution having a concentration of 10 mol/L, wherein the reaction temperature is 50°C, the feeding speed is controlled to be 10 ml/min, the stirring intensity is 500 r/min, and a pH automatic charging machine is used to adjust the precipitator Na2CO3(10mol/L) to have a pH value of 10.5 during the reaction. After the reaction solution stays in the reaction kettle for 1 hour, the product is pumped into the circulation tank from the bottom of the reaction tank, and the reaction solution naturally overflows back into the reaction tank after filling the circulation tank. After 20 hours of stirring and reaction, the final product is filtered, washed and dried to obtain a precursor material Ni0.6C00.2Mn0.2C0O3.
    Example 3 Weigh and take a certain amount of NiSO4, CoS04 and MnSO4 according to a Ni:Co:Mn mole ratio of 0.8:0.1:0.1, dissolve them into deionized water to prepare a mixed salt solution having a concentration of 5 mol/L, and input the mixed salt solution into a reaction kettle of 100 L together with a DL-lactic solution having a concentration of 5 mol/L, wherein the reaction temperature is 80°C, the stirring intensity is controlled to be 1000 r/min, and a pH automatic charging machine is used to adjust the precipitator NaOH (10mol/L) to have a pH value of 11 during the reaction.
    After the reaction solution stays in the reaction kettle for 5 hours, the product is pumped into the circulation tank from the bottom of the reaction tank, and the reaction solution naturally overflows back into the reaction tank after filling the circulation tank.
    After 50 hours of stirring and reaction, the final product is filtered, washed and dried to obtain a precursor material Ni0.8Co0.1Mn0.1 (OH)2. Contrastive Example 1 Weigh and take a certain amount of NiSO4, CoSO4 and MnS04 according to a Ni:Co:Mn mole ratio of 0.5:0.2:0.3, dissolve them into deionized water to prepare a mixed salt solution with a concentration of 0.1 mol/L, and input the mixed salt solution into a reaction kettle of 1 L together with ammonium hydroxide having a concentration of 0.1 mol/L and NaOH solution having a concentration of 0.2 mol/L, wherein the reaction temperature is 30°C, the stirring intensity is controlled to be 300 r/min, and the pH value is adjusted to be 10. The reaction solution naturally overflows and is discharged after filling the reaction kettle.
    After 5 hours of stirring and reaction, a precursor material Ni0.5C00.2Mn0.3(0OH)2 is obtained after being centrifuged, washed and dried.
    Contrastive Example 2 Weigh and take a certain amount of NiC204, CoC204 and MnC204 according to a Ni:Co:Mn mole ratio of 0.6:0.2:0.2, dissolve them into deionized water to prepare a mixed salt solution having a concentration of 10 mol/L, and quickly input the mixed salt solution into a reaction kettle together with ammonium hydroxide having a concentration of 10 mol/L and Na2CQO3 solution having a concentration of 10 mol/L at one time, wherein the reaction temperature is 50°C, and the stirring intensity is 500 r/min.
    After 20 hours of stirring and reaction, a precursor material Ni0.6C00.2Mn0.2C03 is obtained after being centrifuged, washed and dried.
    Mix and sinter the precursor materials obtained in Examples 1-3 according to the technical solution of the present invention and those synthesized in Contrastive
    Examples 1-2 prepared according to the prior art with LIOH at a uniform molar ratio to form a positive electrode material, and assemble R2032 button batteries using a lithium sheet as the negative electrode. 1C discharging specific capacity and circulation retention ratio after 100 cycles are tested at 2.7-4.3V at room temperature.
    The results are shown in Table 1 below: Table 1 Cases Particle Size Tap Density Ni:Co:Mn Mole 1C Capacity D50(um) (g-cm3) Ratio Discharging Retention Specific Ratio Capacity (%) (mAh-g™) Example 1 6.123 2.43 0.49:0.21:0.3 158 85.7 Example 2 8.459 2.52 0.59:0.19:0.22 170.5 86.8 Example 3 12.625 2.60 0.79:0.09:0.12 178.6 89 Contrastive 5.879 2.31 0.46:0.19:0.35 150.2 70.2 Example 1 Contrastive 7.528 2.38 0.57:0.17:0.26 165 65.4 Example 2 Finally, it should be noted that the above are only preferred examples of the present invention, and are not intended to limit the present invention.
    Although the present invention has been explained in detail with reference to the aforementioned examples, one skilled in the art can still modify the technical solutions disclosed in the aforementioned examples, or make equivalent replacements for some parts of the tehnical solutions disclosed in the aforementioned examples.
    Any modification, equivalent replacement, improvement and so on made within the spirit and principle of the present invention should be contained in the protection scope of the present invention.
    Although the embodiments of the present invention have been described above, it will be appreciated that they are not intended to restrict the protection scope of the present invention.
    It should be understood by one skilled in the art that various modifications or variations made on the basis of the technical solutions of the present invention, which cost no creative effort from one skilled in the art, are still within the protection scope of the present invention.
    权利要求:
    Claims (10)
    [1]
    A preparation method of a green and inexpensive ternary material precursor, characterized in that the method comprises: - performing periodic secondary precipitation with a mixed solution comprising nickel salt, manganese salt and cobalt salt, an environmentally friendly complexing agent, and a precipitator as raw material, and the collected product; - returning the product to the periodic secondary precipitation process for a seed crystal circulation; and - removing mother liquor and overflow product after reaction, and obtaining a ternary material precursor after filtering, washing and drying.
    [2]
    The preparation process of a green and inexpensive ternary material precursor according to claim 1, characterized in that it comprises the following steps: - performing a reaction with a mixed solution comprising nickel salt, manganese salt and cobalt salt, an environmentally friendly complexing agent and a precipitator as raw material in the reaction device under inert gas protection; the formed reaction product enters the circulation device and overflows into the reaction device after the circulation device is full of reaction liquid, and the circulation will be repeated; removing the reactor and spilled product after the reaction, and obtaining a ternary material precursor after filtering, washing and drying.
    [3]
    The process of preparing a green and inexpensive ternary material precursor according to claim 1, characterized in that: the environmentally friendly complexing agents are amino carboxylic acids, phosphonates, hydroxyl carboxylic acids, amino acids and polycarboxylic acids.
    [4]
    The preparation process of a green and inexpensive ternary material precursor according to claim 1, characterized in that:
    the precipitator is one of Na 2 CO 3, NaHCO 3, (NH 4) 2 CO 3, NH 4 HCO 3, K 2 CO 3, KHCO 3, NaOH and KOH, or a mixture of some thereof.
    [5]
    The preparation process of a green and inexpensive ternary material precursor according to claim 1, characterized in that: the nickel salt is one of Ni (NO3) 2, NiCl2, NiSO4, NiC2 O4 and (CH3COO) 2Ni, or a mixture of part thereof ; the cobalt salt is one of Co (NO3) 2, CoCl2, CoSO4, CoC2O4 and (CH3COO) 2 CO, or a mixture of part thereof; and the manganese salt is one of Mn (NO3) 2, MnCl2, MnSO4, MnC2O4 and (CH3COO) 2Mn, or a mixture of part thereof.
    [6]
    The process of preparing a green and inexpensive ternary material precursor according to claim 1, characterized in that: the concentration of the mixed salt is 0.1-10 M; the precipitator has a concentration of 0.1-10 mol / L; and the complexing agent has a concentration of 0.1-10 mol / L.
    [7]
    The process of preparing a green and inexpensive ternary material precursor according to claim 1, characterized in that: the pH is maintained at 8-11; the reaction temperature is 30-80 ° C; and the reaction time is 0.1-50 hours.
    [8]
    The preparation process of a green and inexpensive ternary material precursor according to claim 1, characterized in that: the stirring speed during the reaction is 300-1000 r / min, and the feed rate during the reaction is 1-10 ml / min.
    [9]
    Ternary material precursor prepared by the method according to any one of claims 1 to 8, characterized in that: the ternary material precursor is one of NixCoyMn1-x-yCO3 and NixCoyMn1-xy (OH) 2 (0 <x <1.0 <y <1), or a mixture thereof.
    [10]
    A preparation apparatus of a green and inexpensive ternary material precursor, characterized in that it comprises: a reaction tank and a circulation tank, wherein a liquid discharge line at the bottom of the reaction tank is connected to a liquid fill line at the bottom of the circulation tank, an overflow pipe provided at an upper part of the circulation tank is connected to an inlet provided at an upper part of the reaction tank, and the reaction tank and the circulation tank are respectively connected to a plurality of filling devices gas filling devices.
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    同族专利:
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    CN111792679A|2020-10-20|
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    申请号 | 申请日 | 专利标题
    CN202010693147.9A|CN111792679A|2020-07-17|2020-07-17|Green low-cost ternary material precursor and preparation method and device thereof|
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