CN109360983B - Modified high-nickel ternary cathode material and preparation method and application thereof - Google Patents
Modified high-nickel ternary cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a modified high-nickel ternary cathode material and a preparation method and application thereof. The preparation method of the modified high-nickel ternary cathode material comprises the following steps: preparing a high-nickel ternary intermediate phase solution, and dissolving an acidic solid in water to obtain an acidic solution; and uniformly mixing the two solutions, carrying out hydrothermal or solvothermal reaction, calcining, cooling, grinding and sieving to obtain the modified high-nickel ternary cathode material. The preparation method of the modified high-nickel ternary cathode material is simple in process and low in cost, residual alkali on the surface of the high-nickel ternary cathode material can be effectively removed, and the prepared modified high-nickel ternary cathode material has excellent cycling stability; can be widely applied to the ternary cathode material of the nickel battery.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a modified high-nickel ternary cathode material and a preparation method and application thereof.
Background
With the rapid development of the market of power lithium ion batteries, the anode material of the battery gradually becomes the key point of industrial research, wherein the ternary nickel-cobalt-manganese 811 material with high nickel component becomes the hot point of next-step industrialization by virtue of the characteristics of high specific discharge capacity (200mAh/g) and low cost. However, the high-nickel ternary material is easy to absorb water in the slurry mixing and coating processes to cause the slurry to be jelly-like, so that the processing performance is poor, and the performance of the electrode material is influenced, and the higher the nickel content is, the larger the residual alkali content on the surface of the material is, and the industrialization of the material is influenced.
At present, a treatment means for the excessive residual alkali on the surface of the high-nickel ternary material is mainly started from four aspects: (1) generally, the pH value and the production environment of a precursor are controlled from the source, the temperature, the atmosphere and the ambient temperature of the whole production line are controlled, and the contact between a material and air is strictly controlled; (2) in the lithium mixing and sintering stage, the lithium salt proportion is reduced, and the sintering system is adjusted to ensure that lithium can be rapidly diffused into the crystal; (3) the material is washed by water and then sintered for the second time to reduce the content of residual alkali on the surface, but a part of electrical property is correspondingly lost, which is a common method in the current business; (4) surface coating modification is also an effective method for reducing the residual alkali content on the surface of the ternary material, and high-nickel NCM generally needs surface coating.
However, in the prior art, the purpose of reducing residual alkali is achieved by losing capacity by using a processing means with excessive residual alkali on the surface of the high-nickel ternary material, and therefore, a modified high-nickel ternary cathode material is urgently needed to be provided to improve the performance of the electrode material.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide the preparation method of the modified high-nickel ternary cathode material, which can effectively reduce the residual alkali content on the surface of the high-nickel ternary cathode material and obviously improve the cycle stability of the high-nickel ternary cathode material; the invention also aims to provide the modified high-nickel ternary cathode material prepared by the preparation method; the invention also aims to provide application of the modified high-nickel ternary cathode material in a lithium battery cathode material.
The purpose of the invention is realized by the following technical scheme:
on one hand, the invention provides a preparation method of a modified high-nickel ternary cathode material, which comprises the following steps:
dissolving a lithium source in water to prepare a solution A, and dissolving a nickel source, a manganese source and a cobalt source, or dissolving the nickel source, the aluminum source and the cobalt source in deionized water to prepare a solution B; mixing the solution A and the solution B for reaction; in the reaction process, adjusting the pH value of the reaction to be alkalescent, and stirring after the reaction is finished to obtain a high-nickel ternary intermediate phase solution C;
dissolving potassium permanganate in water to obtain a solution D; and adding the solution D into the solution C, stirring, then carrying out hydrothermal reaction or solvothermal reaction, calcining after the reaction is finished, and cooling, grinding and sieving to obtain the modified high-nickel ternary cathode material.
In the above preparation method, preferably, the lithium source may include one or a combination of more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium chloride, lithium fluoride, lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate, and the like.
In the above preparation method, preferably, the nickel source may include one or a combination of more of nickel sulfate, nickel acetate, nickel nitrate, and the like.
In the above preparation method, preferably, the manganese source may include one or a combination of manganese sulfate, manganese acetate, manganese nitrate, and the like.
In the above preparation method, preferably, the aluminum source may include one or more of alumina, aluminum hydroxide, aluminum salt, metaaluminate and the like.
In the above preparation method, preferably, the cobalt source may include one or a combination of more of cobalt sulfate, cobalt acetate, cobalt nitrate, and the like.
In the above preparation method, preferably, in the step one, the pH is 7 to 9; further preferably, the pH is adjusted by ammonia.
In the above preparation method, preferably, in the step one, the reaction is carried out for 2 to 4 hours; the reaction temperature is 50-85 ℃; the stirring time after the reaction is finished is 30-60 min.
In the above production method, preferably, the pH is adjusted to be weakly alkaline by ammonia water; further preferably, the pH is 7-9.
In the above preparation method, preferably, in the second step, the stirring time is 30-60 min; the stirring temperature is 50-85 ℃.
In the above preparation method, preferably, the reaction temperature of the hydrothermal reaction or the solvothermal reaction is 150-.
In the above preparation method, the method preferably further comprises the step of drying by centrifugal washing or evaporating to gel-like drying after the reaction is completed and before the calcination.
In the above-mentioned production method, the solution after the completion of the reaction is preferably stirred and evaporated at 60 to 80 ℃ to form a gel.
In the above production method, the number of times of centrifugation of the solution after completion of the reaction is preferably 1 to 6 times.
In the above preparation method, preferably, the drying is vacuum drying, the temperature of the vacuum drying is 60-100 ℃, and the drying time is 6-12 h.
In the above preparation method, preferably, the solvent used in the solvothermal reaction may include one or a combination of more of ethanol, isopropanol, n-butanol, ethylene glycol, acetone, and the like.
The invention adopts the potassium permanganate, has strong oxidizing ability, difficult deliquescence and good thermal stability, does not introduce impurity ions like other acidic substances, and the Mn element can also play a role in stabilizing the lattice structure of the ternary cathode material.
In the above production method, preferably, the molar ratio of the lithium source, the nickel source, the cobalt source, and the manganese source is 1: x: y: (1-x-y), wherein x is more than or equal to 0.8 and less than 1, y is more than 0 and less than or equal to 0.2, and 1-x-y is not equal to 0; or the molar ratio of the lithium source, the nickel source, the cobalt source and the aluminum source is 1: x: y: (1-x-y), wherein x is more than or equal to 0.8 and less than 1, y is more than 0 and less than or equal to 0.2, and 1-x-y is not equal to 0.
In the preparation method, the concentration of potassium permanganate in the solution D is preferably in the range of 0.1mol/L to 1 mol/L.
In the above preparation method, preferably, the volume ratio of the solution D to the solution C is 1: 5.
In the above preparation method, preferably, in the second step, the calcination process is:
heating the dried mixture to 400-900 ℃ at the heating rate of 3-5 ℃/min in the air or oxygen atmosphere, and preserving the heat for 3-16 h.
On the other hand, the invention also provides the modified high-nickel ternary cathode material prepared by the preparation method.
On the other hand, the invention also provides the application of the modified high-nickel ternary cathode material in a lithium battery cathode material.
The invention has the beneficial effects that:
the preparation method of the modified high-nickel ternary cathode material is simple in process and low in cost, residual alkali on the surface of the high-nickel ternary cathode material can be effectively removed, and the prepared modified high-nickel ternary cathode material has excellent cycling stability.
Drawings
FIG. 1 is a view showing a modified LiNi prepared in example 1 of the present invention0.8Co0.1Mn0.1O2The cycle performance of the cathode material is compared with that of other cathode materials at a rate of 1C.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
This embodiment provides a modified LiNi0.8Co0.1Mn0.1O2The preparation method of the ternary cathode material comprises the following steps:
firstly, 10.7121g of lithium acetate is dissolved in 100ml of deionized water to prepare 1mol/L of lithium acetate solution, 19.9072g of nickel acetate, 2.4509g of manganese acetate and 2.4908g of cobalt acetate are dissolved in the deionized water to prepare 1mol/L of solution, the two solutions are slowly added into a beaker by using a constant flow pump, the pH value is adjusted to be between 7 and 8 by using ammonia water in the reaction process, and the solution is magnetically stirred for 60min after the reaction is finished;
weighing 1.5803g of potassium permanganate solid, dissolving in deionized water to a constant volume of 100ml, and preparing a 0.1mol/L potassium permanganate solution; stirring for 1h at 25 ℃ to form a uniform and stable potassium permanganate solution;
step three, adding 20ml of 0.1mol/L potassium permanganate solution into the mixed reaction solution obtained in the step one, keeping the temperature of the solution at 55 ℃, stirring for 1 hour, then placing the solution into a reaction kettle for hydrothermal reaction at 150 ℃ for 24 hours, after the reaction is finished, centrifugally cleaning for 5 times, and then placing the solution into a vacuum drying oven to dry the solution for 12 hours at 80 ℃ to obtain a mixture; heating the mixture to 800 ℃ at the heating rate of 5 ℃/min in the oxygen atmosphere, preserving the heat for 6h at the temperature, reducing the temperature to normal temperature, grinding and sieving to obtain the modified LiNi0.8Co0.1Mn0.1O2A ternary positive electrode material.
Comparative example 1
This comparative example provides a modified commercially available LiNi0.8Co0.1Mn0.1O2The preparation method of the cathode material comprises the following steps:
weighing 1.5803g of potassium permanganate solid, dissolving in deionized water to a constant volume of 100ml, and preparing a 0.1mol/L potassium permanganate solution; stirring for 1h at 25 ℃ to form a uniform and stable potassium permanganate solution;
step two, 9.728g of commercially available LiNi was weighed out0.8Co0.1Mn0.1O2Dissolving the anode material in 100ml of deionized water to form 1mol/L high-nickel ternary anode material solution;
step three, adding 20ml of 0.1mol/L potassium permanganate solution into the solution obtained in the step two, keeping the temperature of the solution at 55 ℃, stirring for 1 hour, then placing the solution into a reaction kettle for hydrothermal reaction at 150 ℃ for 24 hours, after the reaction is finished, centrifugally cleaning for 5 times, and then placing the solution into a vacuum drying oven for drying at 80 ℃ for 12 hours to obtain a mixture; heating the mixture to 800 ℃ at the heating rate of 5 ℃/min in the oxygen atmosphere, preserving the heat for 6h at the temperature, reducing the temperature to normal temperature, grinding and sieving to obtain the modified commercial LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Table 1 shows modified LiNi prepared in example 10.8Co0.1Mn0.1O2Ternary cathode material, modified commercial LiNi prepared in comparative example 10.8Co0.1Mn0.1O2Ternary positive electrode material, and unmodified commercial LiNi0.8Co0.1Mn0.1O2And (4) comparing the pH value of the ternary cathode material test.
As can be seen from Table 1, the modified LiNi prepared in example 10.8Co0.1Mn0.1O2Ternary cathode materials having a pH reduced from 12.25 to 11.3, are compared to modified, commercially available LiNi0.8Co0.1Mn0.1O2The ternary cathode material is reduced by 0.78.
Table 1:
modified LiNi obtained by example 1 and comparative example 1, respectively0.8Co0.1Mn0.1O2Coating and drying the positive electrode material to assemble a button type lithium ion battery, and carrying out 1C constant current charge and discharge test; and with unmodified LiNi0.8Co0.1Mn0.1O2The cycle performance of the ternary cathode material is shown in fig. 1.
As can be seen from FIG. 1, the modified LiNi in example 10.8Co0.1Mn0.1O2The capacity retention rate of the ternary cathode material lithium ion battery under the multiplying power of 1C is higher than that of the unmodified LiNi0.8Co0.1Mn0.1O2After the ternary cathode material is cycled for 50 weeks, the capacity retention rate of the embodiment 1 is greatly improved from 75.5% to 94.08%, and compared with the comparative example 1, the capacity retention rate of the embodiment 1 is 12.13% higher.
Example 2
This example provides a modified LiNi0.8Co0.1Mn0.1O2The preparation method of the ternary cathode material comprises the following steps:
firstly, 10.7121g of lithium acetate is dissolved in 100ml of deionized water to prepare 1mol/L of lithium acetate solution, 19.9072g of nickel acetate, 2.4509g of manganese acetate and 2.4908g of cobalt acetate are dissolved in the deionized water to prepare 1mol/L of solution, the two solutions are slowly added into a beaker by using a constant flow pump, the pH value is adjusted to be between 7 and 8 by using ammonia water in the reaction process, and the solution is magnetically stirred for 60min after the reaction is finished;
weighing 3.1606g of potassium permanganate solid, dissolving in deionized water to a constant volume of 100ml, and preparing a 0.2mol/L potassium permanganate solution; stirring for 1h at 25 ℃ to form a uniform and stable potassium permanganate solution;
step three, adding 20ml of 0.2mol/L potassium permanganate solution into the mixed reaction solution obtained in the step one, keeping the temperature of the solution at 55 ℃, stirring for 1h, then placing the solution into a reaction kettle for hydrothermal reaction at 150 ℃ for 24h, centrifugally cleaning for 5 times, and then placing the solution into a vacuum kettleDrying in an air drying oven at 80 deg.C for 12 hr to obtain a mixture; heating the mixture to 800 ℃ at the heating rate of 5 ℃/min in the oxygen atmosphere, preserving the heat for 6h at the temperature, reducing the temperature to normal temperature, grinding and sieving to obtain the modified LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Example 3
This example provides a modified LiNi0.8Co0.1Al0.1O2The preparation method of the ternary cathode material comprises the following steps:
firstly, 7.2397g of lithium nitrate is dissolved in 100ml of deionized water to prepare 1mol/L of lithium acetate solution, 23.2648g of nickel nitrate, 3.7531g of aluminum nitrate and 2.9105g of cobalt nitrate are dissolved in the deionized water to prepare 1mol/L of solution, the two solutions are slowly added into a beaker by using a constant flow pump, the pH value is adjusted to be 7-8 by using ammonia water in the reaction process, and the solution is magnetically stirred for 60min after the reaction is finished;
weighing 3.1606g of potassium permanganate solid, dissolving in deionized water to a constant volume of 100ml, and preparing a 0.2mol/L potassium permanganate solution; stirring for 1h at 25 ℃ to form a uniform and stable potassium permanganate solution;
step three, adding 20ml of 0.2mol/L potassium permanganate solution into the mixed reaction solution obtained in the step one, keeping the temperature of the solution at 55 ℃, stirring for 1 hour, then placing the solution into a reaction kettle for hydrothermal reaction at 150 ℃ for 24 hours, centrifugally cleaning for 5 times, and then placing the solution into a vacuum drying oven to dry the solution for 12 hours at 80 ℃ to obtain a mixture; heating the mixture to 800 ℃ at the heating rate of 5 ℃/min in the oxygen atmosphere, preserving the heat for 6h at the temperature, reducing the temperature to normal temperature, grinding and sieving to obtain the modified LiNi0.8Co0.1Al0.1O2And (3) a positive electrode material.
Example 4
This example provides a modified LiNi0.8Co0.1Mn0.1O2The preparation method of the ternary cathode material comprises the following steps:
firstly, 10.7121g of lithium acetate is dissolved in 100ml of ethanol to prepare 1mol/L of lithium acetate solution, 19.9072g of nickel acetate, 2.4509g of manganese acetate and 2.4908g of cobalt acetate are dissolved in the ethanol to prepare 1mol/L of solution, the two solutions are slowly added into a beaker by using a constant flow pump, the pH value is adjusted to be between 7 and 8 by using ammonia water in the reaction process, and the solution is magnetically stirred for 60min after the reaction is finished;
weighing 1.5803g of potassium permanganate solid, dissolving in ethanol to a constant volume of 100ml, and preparing a 0.1mol/L potassium permanganate solution; stirring for 1h at 25 ℃ to form a uniform and stable potassium permanganate solution;
step three, adding 20ml of 0.1mol/L potassium permanganate solution into the mixed reaction solution obtained in the step one, keeping the temperature of the solution at 55 ℃, stirring for 1 hour, then placing the solution into a reaction kettle for solvothermal reaction at 200 ℃ for 12 hours, centrifugally cleaning for 5 times, and then placing the solution into a vacuum drying oven to dry for 6 hours at 100 ℃ to obtain a mixture; heating the mixture to 900 ℃ at the heating rate of 3 ℃/min in the oxygen atmosphere, preserving the heat for 12h at the temperature, reducing the temperature to normal temperature, grinding and sieving to obtain the modified LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Example 5
This embodiment provides a modified LiNi0.9Co0.05Mn0.05O2The preparation method of the cathode material comprises the following steps:
firstly, 7.2398g of lithium acetate is dissolved in 100ml of deionized water to prepare 1mol/L of lithium acetate solution, 22.3974g of nickel acetate, 0.865g of manganese acetate and 1.2454g of cobalt acetate are dissolved in the deionized water to prepare 1mol/L of solution, the two solutions are slowly added into a beaker by using a constant flow pump, the PH is adjusted to be between 7 and 8 by using ammonia water in the reaction process, and the solution is magnetically stirred for 60min after the reaction is finished;
weighing 1.5803g of potassium permanganate solid, dissolving in deionized water to a constant volume of 100ml, and preparing a 0.1mol/L potassium permanganate solution; stirring for 1h at 25 ℃ to form a uniform and stable potassium permanganate solution;
step three, adding 20ml of 0.1mol/L potassium permanganate solution into the mixed reaction solution obtained in the step one, keeping the temperature of the solution at 55 ℃, stirring for 1 hour, then placing the solution into a reaction kettle for hydrothermal reaction at 150 ℃ for 24 hours, after the reaction is finished, centrifugally cleaning for 5 times, and then placing the solution into a vacuum drying ovenDrying at 80 deg.C for 12 hr to obtain mixture; heating the mixture to 800 ℃ at the heating rate of 5 ℃/min in the oxygen atmosphere, preserving the heat for 6h at the temperature, reducing the temperature to normal temperature, grinding and sieving to obtain the modified LiNi0.9Co0.05Mn0.05O2And (3) a positive electrode material.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (14)
1. A preparation method of a modified high-nickel ternary cathode material is characterized by comprising the following steps:
dissolving a lithium source in water to prepare a solution A, and dissolving a nickel source, a manganese source and a cobalt source, or dissolving the nickel source, the aluminum source and the cobalt source in deionized water to prepare a solution B; mixing the solution A and the solution B for reaction; in the reaction process, adjusting the pH value of the reaction to 7-9, and stirring to obtain a high-nickel ternary intermediate phase solution C after the reaction is finished;
dissolving potassium permanganate in water to obtain a solution D; adding the solution D into the solution C, stirring, then carrying out hydrothermal reaction or solvothermal reaction, calcining after the reaction is finished, and cooling, grinding and sieving to obtain a modified high-nickel ternary cathode material; the reaction temperature of the hydrothermal reaction or the solvothermal reaction is 150-200 ℃, and the reaction time is 12-24 h; the calcining process comprises the following steps: heating the dried mixture to 400-900 ℃ at the heating rate of 3-5 ℃/min in the air or oxygen atmosphere, and preserving the heat for 3-16 h;
the lithium source comprises one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium chloride, lithium fluoride, lithium phosphate, lithium hydrogen phosphate and lithium dihydrogen phosphate; the nickel source comprises one or more of nickel sulfate, nickel acetate and nickel nitrate; the manganese source comprises one or more of manganese sulfate, manganese acetate and manganese nitrate in combination; the aluminum source comprises an aluminum salt and/or a meta-aluminate; the cobalt source comprises one or more of cobalt sulfate, cobalt acetate and cobalt nitrate.
2. The method of claim 1, wherein: the pH is adjusted by ammonia.
3. The method of claim 1, wherein: in the first step, the reaction is carried out for 2-4 h; the reaction temperature is 50-85 ℃; the stirring time after the reaction is finished is 30-60 min.
4. The method of claim 1, wherein: in the second step, the stirring time is 30-60 min; the stirring temperature is 50-85 ℃.
5. The method of claim 1, wherein: in the second step, after the reaction is finished and before the calcination, the method also comprises the step of centrifugally washing and drying or evaporating to be gelatinous and drying.
6. The method of claim 5, wherein: the solution after the reaction is stirred and evaporated at the temperature of 60-80 ℃ until the solution is gelatinous.
7. The method of claim 5, wherein: the number of times of centrifugation of the solution after the completion of the reaction was 1 to 6 times.
8. The method of claim 5, wherein: the drying is vacuum drying, the temperature of the vacuum drying is 60-100 ℃, and the drying time is 6-12 h.
9. The method of claim 1, wherein: the solvent adopted by the solvent thermal reaction comprises one or more of ethanol, isopropanol, n-butanol, glycol and acetone.
10. The method of claim 1, wherein: the molar ratio of the lithium source to the nickel source to the cobalt source to the manganese source is 1: x: y: (1-x-y), wherein x is more than or equal to 0.8 and less than 1, y is more than 0 and less than or equal to 0.2, and 1-x-y is not equal to 0; or the molar ratio of the lithium source, the nickel source, the cobalt source and the aluminum source is 1: x: y: (1-x-y), wherein x is more than or equal to 0.8 and less than 1, y is more than 0 and less than or equal to 0.2, and 1-x-y is not equal to 0.
11. The method of claim 1, wherein: the concentration range of potassium permanganate in the solution D is 0.1-1 mol/L.
12. The method of claim 11, wherein: the volume using ratio of the solution D to the solution C is 1: 5.
13. The modified high-nickel ternary cathode material prepared by the preparation method of any one of claims 1 to 12.
14. Use of the modified high-nickel ternary positive electrode material of claim 13 in a positive electrode material for a lithium battery.
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| CN111233052A (en) * | 2020-01-17 | 2020-06-05 | 清华大学深圳国际研究生院 | Nickel cobalt lithium manganate ternary positive electrode material, preparation method thereof, positive electrode and battery |
| CN111675249B (en) * | 2020-06-11 | 2022-09-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of copper-loaded ternary nanobelt cathode material, product and application thereof |
| CN112194197A (en) * | 2020-08-27 | 2021-01-08 | 浙江美都海创锂电科技有限公司 | High-nickel ternary positive electrode material with low internal resistance and low flatulence rate as well as preparation method and application thereof |
| CN112038613A (en) * | 2020-09-17 | 2020-12-04 | 贵州大学 | Modification method for realizing doped coating of high-nickel ternary cathode material by preprocessing precursor |
| CN112499696B (en) * | 2020-11-30 | 2023-01-13 | 蜂巢能源科技有限公司 | Method for reducing residual alkali content of high-nickel material and low-residual alkali high-nickel material prepared by method |
| CN114927682A (en) * | 2022-05-18 | 2022-08-19 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | LiNi ternary material for increasing high nickel content x Co y Mn 1-x-y O 2 Method for cycling stability and safety of anode material |
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