CN107275634B - Method for synthesizing high-tap-density and high-capacity spherical lithium-rich manganese-based positive electrode material without complexing agent - Google Patents
Method for synthesizing high-tap-density and high-capacity spherical lithium-rich manganese-based positive electrode material without complexing agent Download PDFInfo
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a method for synthesizing a high-tap-density and high-capacity spherical lithium-rich manganese-based positive electrode material without a complexing agent, which comprises the following steps of: 1) preparing mixed aqueous solution of soluble salts of nickel, cobalt and manganese and precipitator solution; 2) measuring a precipitator solution, adjusting the pH value of the precipitator solution, and heating; 3) under stirring, mixing a mixed aqueous solution of soluble salts of nickel, cobalt and manganese with a heated precipitator in a parallel flow manner, and carrying out coprecipitation reaction; 4) washing and drying the coprecipitation product to obtain a nickel-cobalt-manganese precipitation precursor; 5) calcining the nickel-cobalt-manganese precipitate precursor to obtain an oxide compound; 6) and uniformly mixing the lithium carbonate and the oxide compound, and pre-calcining and sintering to obtain the lithium carbonate/oxide composite material. By adopting a carbonate coprecipitation method, a sintering process is improved under the condition of no complexing agent, the particle size and the density of a precursor are effectively controlled, and the high-capacity spherical lithium-rich manganese-based positive electrode material with high tap density, high energy density and good rate capability is prepared.
Description
Technical Field
The invention belongs to the preparation of a lithium ion battery anode material, and particularly relates to a method for synthesizing a lithium-rich manganese-based anode material with high tap density and high capacity without a complexing agent.
Background
With the gradual depletion of fossil energy and the environmental issues facing today, green and renewable energy sources are gaining more and more research and attention. The battery is used as a device for quickly realizing mutual conversion of chemical energy and electric energy, and is an important medium for reasonably and effectively utilizing energy. Lithium ion batteries have been widely used in the fields of mobile phones, notebook computers, cameras, etc. because of their advantages of high specific energy, high operating voltage, wide operating temperature range, long storage life, etc. In addition, future Hybrid Electric (HEV) and Electric Vehicle (EV) applications, military and space technology applications, etc. place higher demands on the energy density, power density and cycle life of the battery. Therefore, the development of high-performance (high energy density, long life, safety) and low-cost lithium ion batteries is the key point of the development of the mobile power supply industryAnd hot spots, mainly aiming at developing novel electrode materials suitable for high-performance lithium ion batteries and preparation technology thereof. Recently, lithium-rich manganese-based positive electrode materials (Li)1+x[NiαCoβMnγ]1-xO2wherein, α + β + γ ═ 1) has the advantages of high theoretical capacity, high working voltage, low cost, good safety performance and the like, and is expected to become a new generation of high energy density lithium ion battery anode material.
Throughout the history of lithium ion battery development, it is clear that the development of electrode materials is developed around the need of increasing the energy density (mainly, the volume energy density) of the battery. There are three main approaches to increasing the volumetric energy density of lithium ion batteries: 1) increasing the tap (compacted) density of the positive electrode material; 2) the reversible specific capacity of the anode material is improved; 3) the working voltage of the anode material is improved. In many cases, the three need to be combined. There are two main methods for increasing the tap (compaction) density of the positive electrode material, the first method is to prepare the material into micron-sized single crystal particles (10-20 μm), such as the commercialized LiCoO2And LiMn2O4. However, the materials suitable for the method are few, and other electrode materials containing various active transition metal components, such as nickel-cobalt-manganese ternary layered materials, are difficult to prepare into micron-sized large single crystal particles. In addition, the nickel-cobalt-manganese ternary layered material has poor ionic conductivity, and the electrochemical performance of the nickel-cobalt-manganese ternary layered material is greatly reduced even if the nickel-cobalt-manganese ternary layered material is prepared into micron-sized single crystal particles. In response to this problem, another method for increasing the tap density of the positive electrode material, that is, a micro-spherical material assembled from primary nanoparticles, has been developed. The spherical material not only overcomes the problem of lithium ion diffusion in micron single crystal particles, but also improves the tap density of the material to a great extent. In addition, the micro-spherical material has many other advantages such as excellent flowability, dispersibility, and processability.
At present, the preparation of the micron spherical material with high tap density mainly adopts a coprecipitation method, including a hydroxide coprecipitation method, a carbonate coprecipitation method and an oxalate coprecipitation method, wherein the former two methods are most commonly used and have better effect.The hydroxide coprecipitation method generally uses sodium hydroxide as a precipitant, and the carbonate coprecipitation method uses sodium carbonate as a precipitant, and these two methods have respective advantages. Generally, the hydroxide precipitation method produces spherical materials with large primary particles, high tap density, and small specific surface area. However, hydroxide precipitates are sensitive to air and are easily oxidized, so that active transition metals such as nickel, cobalt and manganese are unevenly distributed in the material in the preparation process, and the electrochemical performance of the material is influenced. Therefore, inert gas is needed for protection in the precipitation process, and the coprecipitation conditions are harsh. In contrast, the carbonate is much more stable in air and has strong oxidation resistance, so that inert gas protection is not needed in the coprecipitation process, and the coprecipitation conditions are mild. At present, a large amount of complexing agents or even surfactants are required to be added in the process of preparing the micron spherical material by a coprecipitation method, and commonly used complexing agents comprise sodium citrate, sodium tartrate, sodium sulfosalicylate and ammonia water, wherein the ammonia water is most widely applied. In fact, these complexing agents are expensive, and large-scale use not only increases the production cost of the materials, but also increases the difficulty of later washing, and the produced sewage has great harm to the environment and high sewage treatment cost. For example, patent application CN103956479A describes a method for preparing a high capacity spherical lithium-rich cathode material. In the preparation process, ammonia water is used as a complexing agent, and the tap density of the prepared material is 1.8g/cm-3Left and right. Patent application CN106410186A describes a method for preparing a lithium-rich layered oxide positive electrode material, which is prepared by a solid phase method, has irregular particle shape and 40-cycle capacity of 240mAh g-1Left and right.
In summary, in the coprecipitation preparation method of the spherical lithium-rich manganese-based cathode material in the prior art, a large amount of complexing agent needs to be added, which not only increases the preparation cost of the cathode material, but also causes the problem of environmental pollution, and an effective solution is not yet available.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for synthesizing a spherical lithium-rich manganese-based positive electrode material with high tap density and high capacity without a complexing agent. Co-precipitating with carbonateThe precipitation method is characterized in that a sintering process is improved under the condition of no complexing agent, the particle size and the density of a precursor are effectively controlled, a high-capacity spherical lithium-rich manganese-based positive electrode material with high tap density, high energy density and good rate performance is prepared, and the tap density of the prepared positive electrode material can reach 2.4g/cm-3。
In order to solve the problems, the technical scheme of the invention is as follows:
a method for synthesizing a spherical lithium-rich manganese-based positive electrode material with high tap density and high capacity without a complexing agent comprises the following steps:
1) preparing a mixed aqueous solution of soluble salts of nickel, cobalt and manganese and a precipitator solution with a set concentration;
2) measuring a set amount of 0.1-0.2mol L-1Adding the precipitant into a reaction kettle as a base solution, and adjusting the pH value of the precipitant to 8.1-8.5 by using acid to obtain L of the precipitant with the concentration of 0.1-0.2mol-1Heating the buffer solution of (1);
3) mixing the mixed water solution of soluble salts of nickel, cobalt and manganese with 2-2.5mol L of stirring-1Adding the precipitant into the heated buffer solution in the step 2) in a concurrent manner, and carrying out coprecipitation reaction, wherein the stirring speed of the coprecipitation reaction is 800-1200rpm, the pH value is 8.1-8.5, and the feeding speed is 200-500mlh-1The reaction time is 8-12 hours;
4) after the reaction is finished, washing the coprecipitation product by using hot water, and drying to obtain a nickel-cobalt-manganese precipitation precursor;
5) calcining the obtained nickel-cobalt-manganese precipitate precursor to obtain an oxide compound;
6) and uniformly mixing the lithium carbonate and the oxide compound, and pre-calcining and sintering to obtain the target product material.
Further, in the step 1), the precipitant is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Further, in the step 1), soluble sulfates of nickel, cobalt and manganese are sulfates or nitrates thereof.
Further, in the step 1), mixing soluble sulfates of nickel, cobalt and manganeseIn the solution, the molar ratio of nickel, cobalt and manganese is determined according to the target compound (Li)1+x(MnaNibCoc)1-xO2Where 0. ltoreq. x.ltoreq.0.2, and a + b + c 1).
Further, in the step 2), the acid is formic acid, acetic acid, propionic acid or butyric acid to adjust the pH value of the buffer solution, and the organic acid is easy to remove in the subsequent calcining process.
Further, in the step 2), the buffer solution is used as a base solution, and the temperature after heating is 50-70 ℃.
Further, in the step 4), the coprecipitation product is washed to be nearly neutral by hot water, and the temperature of the hot water is 40-60 ℃.
Further, in the step 4), the drying temperature of the coprecipitation product is 105-115 ℃, and the drying time is 10-13 h.
Further, in the step 5), the calcining temperature of the nickel-cobalt-manganese precipitation precursor is 450-500 ℃, and the calcining time is 8-14 h.
Further, in the step 6), the pre-calcining temperature is 480-520 ℃, and the pre-calcining time is 1.5-2.5 h.
Further, in the step 6), the sintering temperature is 880-920 ℃, and the temperature rise speed between pre-sintering and sintering is 2 ℃ for min-1. Cooling to obtain the target product material Li1+x(MnaNibCoc)1-xO2Wherein x is more than or equal to 0 and less than or equal to 0.2, and a + b + c is 1.
The spherical lithium-rich manganese-based positive electrode material Li prepared by the preparation method1+x(MnaNibCoc)1-xO2Wherein x is more than or equal to 0 and less than or equal to 0.2, and a + b + c is 1.
The invention has the beneficial effects that:
by adopting a carbonate coprecipitation method, under the condition of no complexing agent, the sintering process is improved, the particle size and the density of a precursor are effectively controlled, and the high-capacity spherical lithium-rich manganese-based positive electrode material Li with high tap density, high energy density and good rate capability is prepared1+x(MnaNibCoc)1-xO2Wherein x is more than or equal to 0 and less than or equal to 0.2, aThe tap density of the positive electrode material can reach 2.4g/cm when + b + c is 1-3。
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
Fig. 1 is an SEM image of a spherical lithium-rich cathode material precursor carbonate prepared by using sulfates of nickel, cobalt, and manganese in example 1.
FIG. 2 shows a high tap density and high capacity spherical lithium-rich manganese-based positive electrode material Li prepared by calcining the precursor prepared in example 11.2Mn0.54Ni0.14Co0.12O2SEM image of (d).
FIG. 3 shows Li as a lithium-rich manganese-based positive electrode material prepared in example 11.2Mn0.54Ni0.14Co0.12O2XRD pattern of (a).
FIG. 4 shows Li as a lithium-rich manganese-based positive electrode material prepared in example 11.2Mn0.54Ni0.14Co0.12O2Cycle performance curve of (a).
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Example 1
Adopting a batch reaction mode to react sulfuric acidManganese, nickel sulfate and cobalt sulfate are prepared into a mixed solution with the total concentration of 2M according to the proportion of 37:7:6, and 200mL of 0.1mol L of the mixed solution is added into a 2L self-made reaction kettle-1Adding acetic acid into the sodium carbonate solution, adjusting the temperature to be about 8.3 ℃, and heating to 60 ℃. Stirring, adding 500ml of sulfate of nickel, cobalt and manganese and 2.1mol L of sulfate-1The 476 milliliters of the sodium carbonate precipitator are added into the reaction kettle in a concurrent flow manner for reaction, the stirring speed in the precipitation process is controlled to be 100-1000rpm, the pH value is controlled to be 8.2-8.5, and the feeding speed is controlled to be 250mL h-1The total reaction time was 12 hours. And (3) after the reaction is finished, washing the precipitation product to be nearly neutral by using hot water, and then drying at 110 ℃ for 12 hours to obtain the nickel-cobalt-manganese precipitation precursor. Calcining the obtained spherical precursor material at 500 ℃ for 8 hours to convert the spherical precursor material into an oxide composite, uniformly mixing lithium carbonate and the oxide composite according to the ratio of lithium ions to transition metals (Li/M ═ 1+ x)/(1-x) in a target product, pre-calcining the spherical precursor material at 500 ℃ for 2 hours in a muffle furnace, then calcining the spherical precursor material at 900 ℃ for 1 hour, and raising the temperature at 2 ℃ for min-1Cooling to obtain the target product material Li1.2Mn0.54Ni0.14Co0.12O2The tap density of the material is 2.4g/cm-3。
Fig. 1 is an SEM image of a precursor carbonate of a spherical lithium-rich cathode material prepared by using sulfates of nickel, cobalt, and manganese in example 1, and it can be seen from the SEM image that a better carbonate precursor material with a spherical morphology can be obtained by optimizing and controlling reaction parameters in a coprecipitation process, the particle size distribution is narrow, and the average particle size is about 14 μm. FIG. 2 shows a high tap density and high capacity spherical lithium-rich manganese-based positive electrode material Li prepared by calcining the precursor prepared in example 11.2Mn0.54Ni0.14Co0.12O2SEM image of (d). FIG. 3 shows Li as a lithium-rich manganese-based positive electrode material prepared in example 11.2Mn0.54Ni0.14Co0.12O2XRD pattern of (a). As can be seen from fig. 2 and 3, sintering under this procedure maintained the spherical shape of the material well, with better crystallinity and lamellar structural integrity.
FIG. 4 shows a lithium-rich manganese-based positive electrode material L prepared in example 1i1.2Mn0.54Ni0.14Co0.12O2Cycle performance curve of (a).
Example 2
Preparing manganese sulfate, nickel sulfate and cobalt sulfate into a mixed solution with the total concentration of 2M according to the proportion of 37:7:6 by adopting a continuous reaction mode, and adding 1000mL of 0.1mol L of the mixed solution into a 10L self-made reaction kettle-1Adding acetic acid into the sodium carbonate solution, adjusting the temperature to be about 8.3 ℃, and heating to 60 ℃. 2.5 liters of sulfate of nickel, cobalt and manganese and 2.1mol L of sulfate are stirred-1The sodium carbonate precipitator (2.38 liters) is added into a reaction kettle in a concurrent flow manner for reaction, the stirring speed in the precipitation process is controlled to be 100-1000rpm, the pH value is controlled to be 8.2-8.5, and the feeding speed is controlled to be 250mL h-1And after the reaction time is 12 hours, discharging until the volume of the bottom liquid in the reaction kettle is 1000ml, and continuing to react. And (3) after the reaction is finished, washing the precipitation product of the multiple reactions to be nearly neutral by using hot water, and then drying at 110 ℃ for 12 hours to obtain the nickel-cobalt-manganese precipitation precursor. Calcining the obtained spherical precursor material at 500 ℃ for 8 hours to convert the spherical precursor material into an oxide compound, uniformly mixing lithium carbonate and the oxide compound according to the ratio of lithium ions to transition metals (Li/M ═ 1+ x)/(1-x), pre-calcining the spherical precursor material in a muffle furnace at 500 ℃ for 2 hours, then calcining the mixture at 900 ℃ for 1 hour, and raising the temperature at 2 ℃ for min-1Cooling to obtain the target product material Li1.2Mn0.54Ni0.14Co0.12O2The tap density of the material is 2.4g/cm-3。
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (9)
1. A method for synthesizing a spherical lithium-rich manganese-based positive electrode material with high tap density and high capacity without a complexing agent is characterized by comprising the following steps: the method comprises the following steps:
1) preparing a mixed aqueous solution of soluble salts of nickel, cobalt and manganese and a precipitator solution with a set concentration;
2) measuring a set amount of 0.1-0.2mol L-1Adding the precipitant into a reaction kettle as a base solution, and adjusting the pH value of the precipitant to 8.1-8.5 by using acid to obtain L of the precipitant with the concentration of 0.1-0.2mol-1Heating the buffer solution of (1);
3) mixing the mixed water solution of soluble salts of nickel, cobalt and manganese with 2-2.5mol L of stirring-1Adding the precipitant into the heated buffer solution in the step 2) in a concurrent manner, and carrying out coprecipitation reaction, wherein the stirring speed of the coprecipitation reaction is 800-1200rpm, the pH value is 8.1-8.5, and the feeding speed is 200-500ml h-1The reaction time is 8-12 hours;
4) after the reaction is finished, washing the coprecipitation product by using hot water, and drying to obtain a nickel-cobalt-manganese precipitation precursor;
5) calcining the obtained nickel-cobalt-manganese precipitate precursor to obtain an oxide compound;
6) uniformly mixing lithium carbonate and an oxide compound, and pre-calcining and sintering to obtain a target product material;
in the step 6), the pre-calcining temperature is 480-520 ℃, and the pre-calcining time is 1.5-2.5 h; the sintering temperature is 880-920 ℃, and the temperature rise speed between the pre-forging and sintering is 2 ℃ for min-1。
2. The method of claim 1, wherein: in the step 1), the precipitant is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
3. The method of claim 1, wherein: in the step 1), soluble sulfates of nickel, cobalt and manganese are sulfates or nitrates thereof.
4. The method of claim 1, wherein: in the step 1), the molar ratio of nickel, cobalt and manganese in the mixed solution of soluble sulfates of nickel, cobalt and manganese is determined according to the target compound Li1+x(MnaNibCoc)1-xO2Where x is 0. ltoreq. x.ltoreq.0.2, and a + b + c is 1.
5. The method of claim 1, wherein: in step 2), formic acid, acetic acid, propionic acid or butyric acid is used for adjusting the pH value of the precipitator.
6. The method of claim 1, wherein: in the step 2), the temperature after heating is 50-70 ℃.
7. The method of claim 1, wherein: in the step 4), the drying temperature of the coprecipitation product is 105-115 ℃, and the drying time is 10-13 h.
8. The method of claim 1, wherein: in the step 5), the calcination temperature of the nickel-cobalt-manganese precipitation precursor is 450-500 ℃, and the calcination time is 8-14 h.
9. The spherical lithium-rich manganese-based cathode material Li prepared by the method of any one of claims 1 to 81+x(MnaNibCoc)1-xO2Wherein x is more than or equal to 0 and less than or equal to 0.2, and a + b + c is 1.
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| CN111498908A (en) * | 2020-04-27 | 2020-08-07 | 中信大锰矿业有限责任公司 | Preparation method of quasi-spherical manganese-rich ternary precursor |
| CN111987305A (en) * | 2020-08-28 | 2020-11-24 | 四川虹微技术有限公司 | Method for preparing high-capacity lithium-rich manganese-based positive electrode material through ammoniation-free coprecipitation |
| CN112786876A (en) * | 2021-03-02 | 2021-05-11 | 昆明理工大学 | Preparation method of lithium-rich lithium battery cathode material with single crystal structure |
| CN114665086A (en) * | 2022-02-18 | 2022-06-24 | 中国科学院青海盐湖研究所 | Lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN114906881A (en) * | 2022-04-29 | 2022-08-16 | 浙江格派钴业新材料有限公司 | Preparation method of cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material |
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