CN112952085A - Gradient high-nickel single crystal ternary material, preparation method thereof and battery using material - Google Patents
Gradient high-nickel single crystal ternary material, preparation method thereof and battery using material Download PDFInfo
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Abstract
The invention relates to a lithium ion battery anode material, and particularly provides a preparation method of a gradient high-nickel single crystal ternary material, wherein the preparation method comprises the following steps: (1) adopting nanometer high nickel ternary material particles as crystal nucleus; (2) the crystal nucleus and a first nickel-containing cobalt-manganese solution carry out a first coprecipitation reaction, a second nickel-containing cobalt-manganese solution is added into the solution after the first coprecipitation reaction is finished to carry out a second coprecipitation reaction, and n times of coprecipitation reaction is carried out according to the method; the nickel content in the first nickel-cobalt-manganese-containing solution to the nth nickel-cobalt-manganese-containing solution is reduced in a gradient manner, and the manganese content is increased in a gradient manner; (3) and mixing the product of the nth coprecipitation reaction, a lithium source and crystal nuclei, and calcining in an oxygen-containing atmosphere. The gradient high-nickel single crystal ternary material prepared by the method has an obvious single crystal form, the structural strength of ternary material particles is effectively improved, the residual alkali amount on the surface of the material is reduced, and the discharge capacity and the cycle performance of the battery can be effectively improved when the material is used for the battery.
Description
Technical Field
The invention relates to a positive active material of a lithium ion battery, in particular to a gradient high-nickel single crystal ternary material, a preparation method thereof and a battery using the material.
Background
With the rapid development of new energy automobiles in recent years, high energy density, long cycle life, high safety performance, low cost and the like become core problems concerned by battery and material related enterprises. The ternary material has the advantages of high specific capacity, good capacity retention rate, good high-voltage bearing and charging performance and the like, and becomes an object pursued by a plurality of enterprises, wherein the high-nickel ternary material is a focus of attention because the energy density of the material is greatly improved.
At present, high-nickel ternary materials on the market are mostly composed of secondary particles and exist in the form of aggregates and polycrystals, so that the compaction density of the materials is low, and agglomerated particles are easily broken in the rolling process and the charge-discharge cycle process, so that the overall performance of the battery is influenced. And the high-nickel ternary material has exposed defects of residual alkali, cation mixed discharge and the like on the particle surface due to the increase of the nickel content, and has great impact on safety performance.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, a high-nickel ternary material is low in compaction density and easy to break in the processes of preparing electrode plates and charging and discharging circulation, and further causes poor cycle performance and safety performance of a battery, and provides a gradient high-nickel single crystal ternary material, a preparation method thereof and a battery using the material.
In order to achieve the aim, the invention provides a preparation method of a gradient high-nickel single crystal ternary material, wherein the preparation method comprises the following steps:
(1) adopting nanometer high nickel ternary material particles as crystal nucleus;
(2) the crystal nucleus and a first nickel-containing cobalt-manganese solution carry out a first coprecipitation reaction, a second nickel-containing cobalt-manganese solution is added into the solution after the first coprecipitation reaction is finished to carry out a second coprecipitation reaction, and n times of coprecipitation reaction is carried out according to the method; the nickel content in the first nickel-cobalt-manganese-containing solution to the nth nickel-cobalt-manganese-containing solution is reduced in a gradient manner, and the manganese content is increased in a gradient manner;
(3) mixing the product of the nth coprecipitation reaction, a lithium source and crystal nucleus, and calcining in an oxygen-containing atmosphere;
wherein n is more than or equal to 3.
The invention also provides a gradient high-nickel single crystal ternary material prepared by the method.
The invention also provides a lithium ion battery anode which comprises the ternary material.
The invention also provides a lithium ion battery which comprises the anode.
The invention also provides a battery pack which is formed by connecting the lithium ion batteries in series and/or in parallel.
The invention also provides a battery power vehicle which comprises the battery pack.
The gradient high-nickel single crystal ternary material prepared by the invention is in a single crystal form, can effectively improve the structural strength of particles and avoid the problem of crushing the material in the use process, and can form a concentration gradient with gradually reduced nickel content and gradually increased manganese content from the core of the particles to the outside, thereby effectively reducing the residual alkali content on the surfaces of the particles, stabilizing the surface structure of the material and improving the cycle performance and safety performance of a battery.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a flow chart of the preparation process of the high nickel single crystal ternary material in example 1;
FIG. 2 is an SEM image of the high-nickel single-crystal ternary material S1 prepared in example 1;
fig. 3 is a graph showing the discharge performance and cycle performance of a battery assembled from the ternary material prepared in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a gradient high-nickel single crystal ternary material, wherein the preparation method comprises the following steps:
(1) adopting nanometer high nickel ternary material particles as crystal nucleus;
(2) the crystal nucleus and a first nickel-containing cobalt-manganese solution carry out a first coprecipitation reaction, a second nickel-containing cobalt-manganese solution is added into the solution after the first coprecipitation reaction is finished to carry out a second coprecipitation reaction, and n times of coprecipitation reaction is carried out according to the method; the nickel content in the first nickel-cobalt-manganese-containing solution to the nth nickel-cobalt-manganese-containing solution is reduced in a gradient manner, and the manganese content is increased in a gradient manner;
(3) mixing the product of the nth coprecipitation reaction, a lithium source and crystal nucleus, and calcining in an oxygen-containing atmosphere;
wherein n is more than or equal to 3.
According to the invention, the nickel content refers to the molar content of nickel element in any one of the first nickel-cobalt-manganese-containing solution to the nth nickel-cobalt-manganese-containing solution in the total metal elements of nickel, cobalt and manganese, and the manganese content refers to the molar content of manganese element in any one of the first nickel-cobalt-manganese-containing solution to the nth nickel-cobalt-manganese-containing solution in the total metal elements of nickel, cobalt and manganese. The term "in this way" in the present invention means that the subsequent coprecipitation reaction is performed by adding a second nickel-containing cobalt-manganese solution to the solution after the first coprecipitation reaction is completed to perform a second coprecipitation reaction. In the coprecipitation process, a small amount of nano-grade high-nickel ternary material particles are selected as crystal nuclei to induce crystallization, so that the generation and agglomeration of new crystal nuclei can be inhibited to a certain extent, and crystals generated by reaction grow in situ on the surfaces of the crystal nuclei, thereby being beneficial to forming precipitates with narrow particle size distribution; forming a concentration gradient with gradually reduced nickel content and gradually increased manganese content at the periphery of the crystal nucleus in the coprecipitation process; and a small amount of crystal nucleus is added in the subsequent calcination process, the precursor and the lithium source are uniformly coated on the surface of the crystal nucleus, and can be completely diffused at a lower calcination temperature, so that the particle growth is promoted, the calcination cost is reduced, and the high-nickel single crystal ternary material with a compact structure is formed.
The object of the present invention has been achieved by the above preparation method, in order to further improve the structural stability of the high nickel single crystal ternary material formed, preferably, the average particle size of the crystal nuclei is 100-200 nm; further preferably, the structural formula of the nanoscale high-nickel ternary material is LiNixCoyMn1-x-yO2Wherein x is 0.8 to 0.95 and y is 0.025 to 0.1, more preferably, the formula LiNi is generally chosen0.8Co0.1Mn0.1O2The high nickel 811 ternary material has wide raw material source and stable performance. In order to further improve the structural stability of the single crystal ternary material, the nanoscale high-nickel ternary material is preferably prepared by ball milling a commercially available high-nickel ternary material (for example, a structural formula of LiNi) to obtain the nanoscale high-nickel ternary material0.8Co0.1Mn0.1O2The particle size of the high nickel 811 ternary material is usually 10-20 μm) is placed in a ball mill, the ball-material ratio is controlled to be 1:10-20, and the high nickel 811 ternary material with the average particle size of 100-200nm is prepared by high-speed ball milling (such as 1000-2000rpm) for 2-3 h. If the size of the crystal nucleus is too small, the crystal nucleus can be automatically agglomerated, and the uniformity of the crystal is influenced; if the size of the crystal nucleus is too large, lithium ion deintercalation paths are increased, and the battery capacity is affected.
According to the invention, in order to further improve the structural stability and uniformity of the prepared material, preferably, in the step (2), the first nickel-containing cobalt manganese solution to the nth nickel-containing cobalt manganese solution which participate in the reaction all adopt complexing solutions; more preferably, the complexing agent used to form the complexing solution is an alkaline solution, and still more preferably aqueous ammonia. In the invention, a first nickel-containing cobalt-manganese solution and an n-th nickel-containing cobalt-manganese solution are prepared into corresponding complexing solutions in advance, and when the complexing solutions are prepared, the molar ratio of the complexing agent ammonia water to the total metal elements of nickel, cobalt and manganese in the nickel-containing cobalt-manganese solution is 1: 1. In the process of coprecipitation reaction, the nickel-containing cobalt-manganese solution is directly added into the reaction in the form of nickel-containing cobalt-manganese complex solution, and then precipitator is slowly added to carry out coprecipitation reaction. By adopting the nickel-cobalt-manganese complex solution, three metal elements can be simultaneously precipitated in the coprecipitation reaction process, and the formed single crystal structure is more uniform and compact. If a complexing solution is not prepared in advance, and a complexing agent is directly added in the coprecipitation reaction process, the coprecipitation is not uniform, and an impurity phase is generated, so that the capacity and the cycle performance of the battery are influenced.
According to the present invention, preferably, in step (2), the conditions of the coprecipitation reaction include: the pH is 10-13 and the temperature is 50-80 ℃.
In the present invention, the coprecipitation reaction further comprises filling a protective gas into the reaction system, and adding a precipitant into the reaction raw material, and the type of the protective gas in the present invention is not particularly limited, and gases such as nitrogen, argon, and the like are generally used. In the process of coprecipitation reaction, a precipitant needs to be slowly added, and the adding speed is preferably to keep the pH of the solution in the reaction process to be 10-13 all the time until the precipitant is added and the reaction is complete. In the present invention, the conditions of the n-time coprecipitation reactions are substantially the same. Preferably, when n is 3, the conditions of the first co-precipitation reaction include: the pH value is 11-13, and the temperature is 60-80 ℃; the conditions of the second coprecipitation reaction include: the pH value is 11-13, and the temperature is 60-80 ℃; the conditions of the third coprecipitation reaction include: the pH value is 11-13, and the temperature is 60-80 ℃.
More preferably, in the step (2), the nickel content of the nth solution containing nickel, cobalt and manganese is reduced by 10% -50% compared with that of the nth-1 solution containing nickel, cobalt and manganese, and the manganese content of the nth solution containing nickel, cobalt and manganese is increased by 40% -50% compared with that of the nth-1 solution containing nickel, cobalt and manganese.
According to the invention, in the first nickel-cobalt-manganese-containing solution, based on the total molar amount of metal elements, the content of nickel is 87-95% and the content of manganese is 3-8% in terms of the elements; in the n-th solution containing nickel, cobalt and manganese, the proportion of nickel is 30-40% and the proportion of manganese is 30-40% in terms of elements based on the total molar weight of metal elements.
Further preferably, n is 3 to 7, more preferably, n is 3.
When n is 3, the first nickel-cobalt-manganese-containing solution contains 87-95% of nickel and 3-8% of manganese by taking the total molar amount of metal elements as a reference; in the second nickel-cobalt-manganese-containing solution, the total molar weight of metal elements is taken as a reference, the content of nickel is 75-85% and the content of manganese is 9-15% in terms of the elements; in the third nickel-cobalt-manganese-containing solution, the content of nickel is 30-40% and the content of manganese is 30-40% in terms of elements based on the total molar weight of metal elements.
According to the invention, the total metal element concentrations of nickel, cobalt and manganese in the first nickel, cobalt and manganese-containing solution to the nth nickel, cobalt and manganese-containing solution are respectively and independently 1-5 mol/L.
In the present invention, the amount of the 1 st to n-th nickel-containing cobalt-manganese solution is preferably: the dosage of the n-th solution containing nickel, cobalt and manganese does not exceed the dosage of any solution from the 1 st solution containing nickel, cobalt and manganese to the (n-1) th solution containing nickel, cobalt and manganese; preferably, the amount of the 1 st to the n th nickel-containing cobalt-manganese solution is 0.1 to 30L, more preferably 0.3 to 20L, and still more preferably 0.5 to 10L.
According to the invention, the gradient thicknesses of the finally formed gradient single crystal are different by adjusting the dosage of the 1 st nickel-cobalt-manganese-containing solution to the nth nickel-cobalt-manganese-containing solution, the dosage of the 1 st nickel-cobalt-manganese-containing solution to the n-1 st nickel-cobalt-manganese-containing solution is more to provide relatively higher nickel concentration, and the dosage of the nth nickel-cobalt-manganese-containing solution is less, so that the residual alkali on the surface of the single crystal is reduced, the surface structure is stable, and the whole single crystal has certain strength and is not easy to break.
According to the invention, in the step (2), the addition amount of the crystal nucleus is 1-5% of the total weight of all nickel-cobalt-manganese salt in the nickel-cobalt-manganese-containing solution based on the input amount, and the single crystal obtained by adding the crystal nucleus according to the proportion is more uniform and stable.
Further preferably, in the step (2), the solution after the nth coprecipitation reaction is completed further comprises an aging treatment, wherein the aging treatment is performed for 10-20 hours at a temperature of 50-80 ℃. And (3) filtering, washing and drying the aged solution to obtain a product, wherein the product is the product of the nth coprecipitation reaction in the step (3). In the present invention, the processes of filtration, washing and drying are not particularly limited, and a conventional method in the prior art may be used.
According to the invention, in step (3), the calcination conditions include: the first stage is heated to 400-600 ℃ for calcination for 2-6h, the second stage is heated to 700-900 ℃ for calcination for 8-16h, the heating rate of the first stage is 5-10 ℃/min, and the heating rate of the second stage is 5-10 ℃/min.
According to the invention, in the step (3), the addition amount of the crystal nucleus is 1-5% of the total weight of the product of the nth coprecipitation reaction; calculated by elements, the molar ratio of the addition amount of the lithium source to the total amount of nickel, cobalt and manganese in the product of the nth coprecipitation reaction is 1-1.3: 1;
preferably, the nickel cobalt manganese salt in the nickel cobalt manganese solution is present in the form of at least one of sulfate, nitrate and acetate;
preferably, a precipitator is added in the coprecipitation reaction, and the precipitator is at least one of sodium hydroxide, lithium hydroxide and potassium hydroxide;
preferably, the lithium source is lithium carbonate and/or lithium hydroxide.
According to the method, the nanometer high-nickel ternary material particles are used as crystal nuclei, the crystal growth is controlled through coprecipitation and calcination, the gradient high-nickel single-crystal ternary material with gradually reduced nickel content and gradually increased manganese content is formed, the single-crystal ternary material is high in compaction density, low in surface residual alkali content and convenient to process, and the capacity, the cycle performance and the safety performance of the battery can be effectively improved by assembling the single-crystal ternary material into the battery.
The invention also provides a gradient high-nickel single crystal ternary material prepared by the preparation method.
Wherein the structural formula of the ternary material is LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.5 and less than or equal to 0.85, and y is more than or equal to 0.05 and less than or equal to 0.3; preferably, the ternary material has a structural formula of LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.6 and less than or equal to 0.81, and y is more than or equal to 0.09 and less than or equal to 0.16;
preferably, the size of the ternary material is 5-10 μm.
According to the invention, the average size of the gradient high-nickel single crystal ternary material prepared by the method can be controlled to be 5-10 μm, the nickel content in the single crystal is reduced in a gradient manner from inside to outside, the manganese content is increased in a gradient manner, and the structure is uniform and stable.
The invention also provides a lithium ion battery anode which comprises the ternary material.
According to the invention, the method for preparing the lithium ion battery anode by using the ternary material is not particularly limited, and the lithium ion battery anode can be prepared by a conventional method. Preferably, the ternary material is mixed with a conductive agent (such as conductive carbon black), a binder (for example PVDF) in a mass ratio of 94: (3-4): and (3-4) homogenizing and coating the pole piece. The ternary material prepared by the invention still keeps stable structure in pole piece homogenizing and coating processes, and the phenomena of particle breakage and the like can not occur.
The invention also provides a lithium ion battery which comprises the anode.
The method for assembling the positive electrode into the lithium ion battery according to the present invention is not particularly limited, and the positive electrode may be assembled by a conventional method in the art.
The invention also provides a battery pack which is formed by connecting the lithium ion batteries in series and/or in parallel.
According to the invention, if the capacity of the lithium ion batteries used alone is not enough, the lithium ion batteries can be assembled in series and/or in parallel to form a battery pack for use.
The invention also provides a battery power vehicle which comprises the battery pack.
According to the invention, the battery powered vehicle mainly refers to a pure electric vehicle or a hybrid electric vehicle, which can adopt a battery pack as a power system, or adopt the battery pack and an internal combustion engine as a hybrid power system, as long as the battery powered vehicle comprises the battery pack.
The gradient high-nickel single crystal ternary material provided by the invention has better structural strength, can effectively reduce the residual alkali amount on the surface of material particles, stabilizes the surface structure of the material, and can improve the capacity and the cycling stability of a battery and the safety performance by assembling the material into the battery.
The present invention will be described in detail below by way of examples.
The starting materials used in the following examples and comparative examples are commercially available unless otherwise specified.
Example 1
This example is used to illustrate the gradient high nickel single crystal ternary material and the preparation method thereof. The preparation process is shown in figure 1, and comprises the following specific steps:
(1) putting a high-nickel 811 ternary material sold in the market into a ball mill, controlling the ball-material ratio to be 1:15, controlling the rotating speed to be 1500rpm, and carrying out ball milling for 3h to obtain high-nickel ternary material particles with the average particle size of 150nm, wherein the high-nickel ternary material particles are used as crystal nuclei for later use;
(2) respectively weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of nickel, cobalt and manganese of 9:0.5:0.5 by taking the total molar amount of metal elements as a reference and adding the nickel sulfate, cobalt sulfate and manganese sulfate into deionized water by taking the total molar amount of the metal elements as an element, preparing a first nickel-containing cobalt-manganese solution with the total metal element concentration of nickel, cobalt and manganese of 2mol/L, and dropwise adding 2mol/L ammonia water into the first nickel-containing cobalt-manganese solution to ensure that NH is generated3·H2The molar ratio of the total mole of the O and the nickel-cobalt-manganese metal elements is 1:1, so as to form a first nickel-cobalt-manganese containing complex solution;
respectively weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of nickel, cobalt and manganese of 8:1:1 by taking the total molar amount of metal elements as a reference, adding the nickel sulfate, the cobalt sulfate and the manganese sulfate into deionized water to prepare a second nickel-containing cobalt-manganese solution with the total metal element concentration of nickel, cobalt and manganese of 2mol/L, and dropwise adding 2mol/L ammonia water into the second nickel-containing cobalt-manganese solution to enable NH3·H2The molar ratio of the total mole of the O and the nickel-cobalt-manganese metal elements is 1:1, so as to form a second nickel-cobalt-manganese containing complex solution;
respectively weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of nickel, cobalt and manganese of 1:1:1 by taking the total molar amount of metal elements as a reference, adding the nickel sulfate, the cobalt sulfate and the manganese sulfate into deionized water to prepare a third nickel-containing cobalt-manganese solution with the total metal element concentration of nickel, cobalt and manganese of 2mol/L, and dropwise adding 2mol/L ammonia water into the third nickel-containing cobalt-manganese solution to enable NH3·H2The molar ratio of the total mole of the O and the nickel-cobalt-manganese metal elements is 1:1, so as to form a third nickel-cobalt-manganese containing complex solution;
adding 3L of first nickel-containing cobalt-manganese complex solution into a reaction kettle, adding 30g of crystal nucleus, introducing nitrogen into the reaction kettle, stirring, controlling the reaction temperature to be 60 ℃, slowly adding 3L of lithium hydroxide solution with the concentration of 2mol/L into the reaction kettle, and controlling the pH value of the solution to be always kept at 12 until the lithium hydroxide solution is completely added to obtain a first reaction solution;
adding 3L of second nickel-containing cobalt-manganese complex solution into the first reaction solution, wherein the reaction temperature is 60 ℃, slowly adding 3L of lithium hydroxide solution with the concentration of 2mol/L into the reaction kettle, and controlling the pH value of the solution to be always kept at 12 until the lithium hydroxide solution is completely added to obtain a second reaction solution;
adding 0.5L of third nickel-containing cobalt-manganese complex solution into the second reaction solution, wherein the reaction temperature is 60 ℃, slowly adding 0.5L of lithium hydroxide solution with the concentration of 2mol/L into the reaction kettle, and controlling the pH value of the solution to be always kept at 12 until the lithium hydroxide solution is completely added to obtain a third reaction solution;
aging the third reaction solution at 60 ℃ for 15h, filtering the solution, washing the solution with deionized water for 4 times, and drying the solution in a vacuum drying oven at 90 ℃ for 4h to obtain a precursor;
(3) in the precursor obtained in the step (2), according to the ratio of Li: adding lithium hydroxide according to the molar ratio of (Ni + Co + Mn) of 1:1, adding crystal nuclei according to 3% of the total weight of the precursor, uniformly mixing, calcining in an oxygen atmosphere, heating to 400 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4h, heating to 750 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 12h, and cooling to room temperature to obtain the compound LiNi with the structural formula of0.810Co0.095Mn0.095O2The gradient high nickel single crystal ternary material S1.
The SEM image of the gradient high-nickel single crystal ternary material S1 is shown in figure 2, and a obvious single crystal can be seen from figure 2, the single crystal grain size is 5-10 mu m, and the crystal form is complete.
The discharge curve of the button cell formed by assembling ternary material S1 is shown in fig. 3.
Example 2
This example is used to illustrate the gradient high nickel single crystal ternary material and the preparation method thereof.
(1) Putting a high-nickel 811 ternary material sold in the market into a ball mill, controlling the ball-material ratio to be 1:20, controlling the rotating speed to be 2000rpm, and carrying out ball milling for 2h to obtain high-nickel ternary material particles with the average particle size of 100nm, wherein the high-nickel ternary material particles are used as crystal nuclei for later use;
(2) respectively weighing nickel acetate, cobalt acetate and manganese acetate according to the molar ratio of nickel, cobalt and manganese of 9:0.5:0.5 by taking the total molar amount of metal elements as a reference and by taking the total molar amount of the metal elements as an element, adding the nickel acetate, the cobalt acetate and the manganese acetate into deionized water to prepare a first nickel-containing cobalt-manganese solution with the total metal element concentration of nickel, cobalt and manganese of 1mol/L, and dropwise adding 2mol/L ammonia water into the first nickel-containing cobalt-manganese solution to ensure that NH is generated3·H2The molar ratio of the total mole of the O and the nickel-cobalt-manganese metal elements is 1:1, so as to form a first nickel-cobalt-manganese containing complex solution;
respectively weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of nickel, cobalt and manganese of 8:1:1 by taking the total molar amount of metal elements as a reference, adding the nickel sulfate, the cobalt sulfate and the manganese sulfate into deionized water to prepare a second nickel-containing cobalt-manganese solution with the total metal element concentration of nickel, cobalt and manganese of 1mol/L, and dropwise adding 2mol/L ammonia water into the second nickel-containing cobalt-manganese solution to enable NH3·H2The molar ratio of the total mole of the O and the nickel-cobalt-manganese metal elements is 1:1, so as to form a second nickel-cobalt-manganese containing complex solution;
respectively weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of nickel, cobalt and manganese of 1:1:1 by taking the total molar amount of metal elements as a reference, adding the nickel sulfate, the cobalt sulfate and the manganese sulfate into deionized water to prepare a third nickel-containing cobalt-manganese solution with the total metal element concentration of nickel, cobalt and manganese of 1mol/L, and dropwise adding 2mol/L ammonia water into the third nickel-containing cobalt-manganese solution to enable NH3·H2The molar ratio of the total mole of the O and the nickel-cobalt-manganese metal elements is 1:1, so as to form a third nickel-cobalt-manganese containing complex solution;
adding 4L of first nickel-containing cobalt-manganese complex solution into a reaction kettle, adding 24g of crystal nucleus, introducing nitrogen into the reaction kettle, stirring, controlling the reaction temperature to be 70 ℃, slowly adding 5.4L of lithium hydroxide solution with the concentration of 1mol/L into the reaction kettle, and controlling the pH value of the solution to be always kept at 11 until the lithium hydroxide solution is completely added to react to obtain a first reaction solution;
adding 6L of second nickel-containing cobalt-manganese complex solution into the first reaction solution, wherein the reaction temperature is 70 ℃, slowly adding 8L of lithium hydroxide solution with the concentration of 1mol/L into the reaction kettle, and controlling the pH value of the solution to be always kept at 11 until the lithium hydroxide solution is completely added to react to obtain a second reaction solution;
adding 1L of third nickel-containing cobalt-manganese complex solution into the second reaction solution, wherein the reaction temperature is 70 ℃, slowly adding 1.34L of lithium hydroxide solution with the concentration of 1mol/L into the reaction kettle, and controlling the pH of the solution to be always kept at 11 until the lithium hydroxide solution is completely added to obtain a third reaction solution;
aging the third reaction solution at 70 ℃ for 12h, filtering the solution, washing the solution with deionized water for 4 times, and drying the solution in a vacuum drying oven at 90 ℃ for 4h to obtain a precursor;
(3) in the precursor obtained in the step (2), according to the ratio of Li: adding lithium hydroxide according to the molar ratio of (Ni + Co + Mn) of 1:1, adding crystal nuclei according to 2% of the total weight of the precursor, uniformly mixing, calcining in an oxygen atmosphere, heating to 500 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 4h, heating to 800 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 12h, and cooling to room temperature to obtain the compound LiNi with the structural formula of0.794Co0.103Mn0.103O2The gradient high nickel single crystal ternary material S2.
Example 3
This example is used to illustrate the gradient high nickel single crystal ternary material and the preparation method thereof.
(1) Putting a high-nickel 811 ternary material sold in the market into a ball mill, controlling the ball-material ratio to be 1:10, controlling the rotating speed to be 1000rpm, and carrying out ball milling for 3h to obtain high-nickel ternary material particles with the average particle size of 150nm, wherein the high-nickel ternary material particles are used as crystal nuclei for later use;
(2) respectively weighing nickel nitrate, cobalt nitrate and manganese nitrate according to the molar ratio of nickel, cobalt and manganese of 9:0.5:0.5 by taking the total molar amount of metal elements as a reference and by taking the total molar amount of the metal elements as an element, adding the nickel nitrate, the cobalt nitrate and the manganese nitrate into deionized water to prepare a first nickel-containing cobalt-manganese solution with the total metal element concentration of nickel, cobalt and manganese of 2mol/L, and dropwise adding 2mol/L ammonia water into the first nickel-containing cobalt-manganese solution to ensure that NH is generated3·H2The molar ratio of the total mole of the O and the nickel-cobalt-manganese metal elements is 1:1, so as to form a first nickel-cobalt-manganese containing complex solution;
based on the total molar amount of metal elements and calculated by the elements,respectively weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of nickel, cobalt and manganese of 6:2:2, adding the nickel sulfate, cobalt sulfate and manganese sulfate into deionized water to prepare a second nickel-cobalt-manganese-containing solution with the total metal element concentration of nickel, cobalt and manganese of 2mol/L, and dropwise adding 2mol/L ammonia water into the second nickel-cobalt-manganese-containing solution to ensure that NH is added3·H2The molar ratio of the total mole of the O and the nickel-cobalt-manganese metal elements is 1:1, so as to form a second nickel-cobalt-manganese containing complex solution;
respectively weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of nickel, cobalt and manganese of 1:1:1 by taking the total molar amount of metal elements as a reference, adding the nickel sulfate, the cobalt sulfate and the manganese sulfate into deionized water to prepare a third nickel-containing cobalt-manganese solution with the total metal element concentration of nickel, cobalt and manganese of 2mol/L, and dropwise adding 2mol/L ammonia water into the third nickel-containing cobalt-manganese solution to enable NH3·H2The molar ratio of the total mole of the O and the nickel-cobalt-manganese metal elements is 1:1, so as to form a third nickel-cobalt-manganese containing complex solution;
adding 6L of first nickel-containing cobalt-manganese complex solution into a reaction kettle, adding 14g of crystal nucleus, introducing nitrogen into the reaction kettle, stirring, controlling the reaction temperature to be 80 ℃, slowly adding 6L of lithium hydroxide solution with the concentration of 2mol/L into the reaction kettle, and controlling the pH value of the solution to be kept at 13 all the time until the lithium hydroxide solution is completely added to obtain a first reaction solution;
adding 10L of second nickel-containing cobalt-manganese complex solution into the first reaction solution, wherein the reaction temperature is 80 ℃, slowly adding 10L of lithium hydroxide solution with the concentration of 2mol/L into the reaction kettle, and controlling the pH value of the solution to be always kept at 13 until the lithium hydroxide solution is completely added to obtain a second reaction solution;
adding 2L of third nickel-containing cobalt-manganese complex solution into the second reaction solution, wherein the reaction temperature is 80 ℃, slowly adding 2L of lithium hydroxide solution with the concentration of 2mol/L into the reaction kettle, and controlling the pH value of the solution to be always kept at 13 until the lithium hydroxide solution is completely added to obtain a third reaction solution;
aging the third reaction solution at 80 ℃ for 20h, filtering the solution, washing the solution with deionized water for 4 times, and drying the solution in a vacuum drying oven at 90 ℃ for 4h to obtain a precursor;
(3) in the precursor obtained in step (2) according toLi: adding lithium hydroxide according to the molar ratio of (Ni + Co + Mn) of 1:1, adding crystal nuclei according to 5% of the total weight of the precursor, uniformly mixing, calcining in an oxygen atmosphere, heating to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 6h, heating to 900 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 16h, and cooling to room temperature to obtain the compound LiNi with the structural formula of0.67Co0.165Mn0.165O2The gradient high nickel single crystal ternary material S3.
Example 4
This example is used to illustrate the gradient high nickel single crystal ternary material and the preparation method thereof.
Compared with the example 1, the difference is that:
in the coprecipitation reaction process, 3L of first nickel-containing cobalt-manganese complex solution is added into a reaction kettle to carry out first coprecipitation reaction to obtain a first reaction solution; adding 5L of second nickel-containing cobalt-manganese complex solution into the first reaction solution to perform a second coprecipitation reaction to obtain a second reaction solution; and adding 6L of third nickel-containing cobalt-manganese complex solution into the second reaction solution to perform a third coprecipitation reaction to obtain a third reaction solution, and further obtaining the gradient high-nickel single crystal ternary material S4.
Example 5
This example is used to illustrate the gradient high nickel single crystal ternary material and the preparation method thereof.
Compared with the example 1, the difference is that:
in the process of coprecipitation reaction, adding 30L of first nickel-containing cobalt-manganese complex solution into a reaction kettle to perform first coprecipitation reaction to obtain a first reaction solution; adding 30L of second nickel-containing cobalt-manganese complex solution into the first reaction solution to perform a second coprecipitation reaction to obtain a second reaction solution; and adding 30L of third nickel-containing cobalt-manganese complex solution into the second reaction solution to perform a third coprecipitation reaction to obtain a third reaction solution, and further obtaining the gradient high-nickel single crystal ternary material S5.
Example 6
This example is used to illustrate the gradient high nickel single crystal ternary material and the preparation method thereof.
The process according to example 1, with the difference that: the average grain diameter of the crystal nucleus is 50nm, so that the gradient high-nickel single crystal ternary material S6 is obtained.
Example 7
This example is used to illustrate the gradient high nickel single crystal ternary material and the preparation method thereof.
The process according to example 1, with the difference that: the average grain diameter of the crystal nucleus is 800nm, thereby obtaining the gradient high-nickel single crystal ternary material S7.
Comparative example 1
The process according to example 1, with the difference that: the average grain diameter of the crystal nucleus is 1.5 mu m, thereby obtaining the gradient high-nickel single crystal ternary material D1.
Comparative example 2
The process according to example 1, with the difference that: and (4) not adding crystal nuclei in the step (3), thereby obtaining the gradient high-nickel single crystal ternary material D2.
Test example
Homogenizing ternary materials S1-S7 and D1-D2 respectively with a conductive agent SP (conductive carbon black Super P) and a binder PVDF according to the mass ratio of 94:3:3, and coating the pole pieces. And assembling the prepared pole piece and a metal lithium piece into a CR2032 type button cell, and carrying out material electrochemical performance test, wherein the voltage range of the power-on test is 2.75-4.2V. The specific discharge capacity at 0.2C and the capacity retention rate at 1C for 100 cycles of the batteries manufactured in each of the examples and comparative examples are shown in table 1.
TABLE 1
The comparison shows that the gradient high-nickel ternary material prepared by the method has obvious single crystal particles, uniform and full crystals, good capacity exertion and cycle life, and the calcining temperature is lower than that of the conventional preparation method, so that the preparation cost can be effectively reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. A preparation method of a gradient high-nickel single crystal ternary material comprises the following steps:
(1) adopting nanometer high nickel ternary material particles as crystal nucleus;
(2) the crystal nucleus and a first nickel-containing cobalt-manganese solution carry out a first coprecipitation reaction, a second nickel-containing cobalt-manganese solution is added into the solution after the first coprecipitation reaction is finished to carry out a second coprecipitation reaction, and n times of coprecipitation reaction is carried out according to the method; the nickel content in the first nickel-cobalt-manganese-containing solution to the nth nickel-cobalt-manganese-containing solution is reduced in a gradient manner, and the manganese content is increased in a gradient manner;
(3) mixing the product of the nth coprecipitation reaction, a lithium source and crystal nucleus, and calcining in an oxygen-containing atmosphere;
wherein n is more than or equal to 3.
2. The preparation method according to claim 1, wherein the average particle size of the crystal nuclei is 100-200 nm;
preferably, the structural formula of the nanoscale high-nickel ternary material is LiNixCoyMn1-x-yO2Wherein x is 0.8-0.95 and y is 0.025-0.1;
further preferably, the crystal nucleus is prepared by ball milling of a high-nickel ternary material.
3. The production method according to claim 1 or 2, wherein in the step (2), the first nickel-containing cobalt-manganese solution to the n-th nickel-containing cobalt-manganese solution participating in the reaction are all complex solutions;
preferably, the complexing agent used to form the complexing solution is an alkaline solution.
4. The production method according to any one of claims 1 to 3, wherein in the step (2), the conditions of the coprecipitation reaction include: the pH is 10-13 and the temperature is 50-80 ℃.
5. The method according to any one of claims 1 to 4, wherein in the step (2), the nickel content of the n-th solution containing nickel, cobalt and manganese is reduced by 10% to 50% compared with that of the n-1-th solution containing nickel, cobalt and manganese, and the manganese content of the n-th solution containing nickel, cobalt and manganese is increased by 40% to 50% compared with that of the n-1-th solution containing nickel, cobalt and manganese;
preferably, the total metal element concentrations of nickel, cobalt and manganese of the first nickel, cobalt and manganese-containing solution to the nth nickel, cobalt and manganese-containing solution are respectively and independently 1-5 mol/L.
6. The production method according to any one of claims 1 to 4, wherein the amount of the n-th nickel-containing cobalt-manganese solution is less than the amount of any one of the 1-th to n-1-th nickel-containing cobalt-manganese solutions;
preferably, the amount of the 1 st to the n th nickel-containing cobalt-manganese solution is 0.1 to 30L, more preferably 0.3 to 20L, and still more preferably 0.5 to 10L.
7. The production method according to any one of claims 1 to 4, wherein in the step (2), the addition amount of the crystal nuclei is 1 to 5% by weight based on the total weight of the nickel-cobalt-manganese salt in all the nickel-cobalt-manganese-containing solutions.
8. The preparation method according to any one of claims 1 to 4, wherein in the step (2), the solution after the nth coprecipitation reaction is completed further comprises an aging treatment, wherein the aging treatment is performed for 10 to 20 hours at a temperature of 50 to 80 ℃.
9. The production method according to any one of claims 1 to 4, wherein in step (3), the calcination conditions include: the first stage is heated to 400-600 ℃ for calcination for 2-6h, the second stage is heated to 700-900 ℃ for calcination for 8-16h, the heating rate of the first stage is 5-10 ℃/min, and the heating rate of the second stage is 5-10 ℃/min.
10. The preparation method according to any one of claims 1 to 4, wherein in the step (3), the addition amount of the crystal nuclei is 1 to 5% of the total weight of the product of the n-th coprecipitation reaction; calculated by elements, the molar ratio of the addition amount of the lithium source to the total amount of nickel, cobalt and manganese in the product of the nth coprecipitation reaction is 1-1.3: 1;
preferably, the nickel cobalt manganese salt in the nickel cobalt manganese solution is present in the form of at least one of sulfate, nitrate and acetate;
preferably, a precipitator is added in the coprecipitation reaction, and the precipitator is at least one of sodium hydroxide, lithium hydroxide and potassium hydroxide;
preferably, the lithium source is lithium carbonate and/or lithium hydroxide.
11. The gradient high-nickel single crystal ternary material prepared by the preparation method of any one of claims 1 to 10.
12. The ternary material of claim 11 wherein the ternary material has the formula LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.5 and less than or equal to 0.85, and y is more than or equal to 0.05 and less than or equal to 0.3;
preferably, the size of the ternary material is 5-10 μm.
13. A lithium ion battery positive electrode comprising the ternary material of claim 11 or 12.
14. A lithium ion battery comprising the positive electrode of claim 13.
15. A battery pack consisting of the lithium ion cells of claim 14 connected in series and/or in parallel.
16. A battery powered vehicle comprising the battery pack of claim 15.
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