CN111370683B - Preparation method of mono-like nickel cobalt lithium manganate - Google Patents
Preparation method of mono-like nickel cobalt lithium manganate Download PDFInfo
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Abstract
The invention provides a preparation method of monocrystal-like nickel cobalt lithium manganate, which comprises the following steps: the first step is as follows: preparing a transition metal salt solution, adding a complexing agent or preparing a complexing agent solution, and preparing a pH adjusting solution; the second step is that: preparing nickel-cobalt-manganese metal precipitate: continuously pumping various solutions prepared in the first step into a reaction kettle through different feeding pipes, connecting a reactor filled with manganese salt with a feeding hole of the reaction kettle, introducing protective gas, heating, continuously adding an oxidant into the reactor, reacting, adjusting the flow of the protective gas, bringing manganese oxide generated by the reaction into the reaction kettle, controlling the pH value in the reaction kettle to perform precipitation reaction, and obtaining nickel-cobalt-manganese metal precipitate after the reaction is finished; the third step: pre-sintering to prepare a nickel-cobalt-manganese precursor; the fourth step: lithiation and sintering to obtain the monocrystal-like nickel cobalt lithium manganate cathode material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a preparation method of mono-like nickel cobalt lithium manganate.
Background
The anode materials which are industrialized at present mainly comprise LiCoO2, LiFePO4, Li2MnO4 and ternary anode materials. Among them, the nickel-cobalt-manganese ternary material is one of the hot spots in the research of the new generation of lithium ion ternary positive electrode material. However, the ternary cathode materials produced by manufacturers at home and abroad are secondary spherical particles formed by agglomeration of fine grains (namely primary particles), and have the following defects: 1. voids exist inside the particles, reducing the compacted density; 2. the particle size is too large, the structure is unstable and is not pressure-resistant, and the particles are easy to break, so that the cyclicity is poor; 3. the inside of the particle is in disordered growth, and the rate performance of the material is low.
In order to solve the above problems, the prior art provides a method for preparing a single crystal ternary cathode material, such as CN104979546B, CN106159251A, CN106450282A, and the like. The current method for synthesizing the monocrystal-like lithium nickel cobalt manganese oxide mainly comprises spray drying, coprecipitation, a high-temperature solid phase method and the like, wherein the main method is to synthesize a precursor through coprecipitation, and the coprecipitation method is to synthesize the monocrystal-like lithium nickel cobalt manganese oxide through small-granularity and large-granularity crushing.
The synthetic monocrystal-like nickel cobalt lithium manganate has the following defects:
firstly, the method comprises the following steps: the small particle size has strict requirements on reaction conditions in the synthesis process, and when the particle size is too small, the specific surface is large, so that precursor particles are agglomerated, internal gaps with poor sphericity are increased, and the subsequent calcination process can cause the particle size of a finished product to be too large and the diameter distance to be too wide, the growth time of the small particle size is short, and the crystallinity and the orderliness of the precursor are poor.
Secondly, the method comprises the following steps: the small-particle precursor prepared by the conventional method has overlarge specific surface and larger surface energy than that of a large-particle precursor, so that agglomeration can be generated before sintering, particles of the agglomerated precursor can be in a splicing shape after sintering, and due to the fact that the agglomeration generates a large particle size distribution distance, a coating dead angle can be generated in subsequent processes such as coating, and the particle consistency is poor. And because the particle strength of the particles generated after agglomeration is not high as that of the precursor particles grown in situ, the particles can be crushed in a rolling step in the subsequent application process of preparing the battery, a non-coating interface is exposed, the surface of the non-coating particles can generate side reaction with electrolyte, serious consequences such as battery swelling and gas expansion can be caused, and the cycling stability of the material is greatly reduced.
Thirdly, the method comprises the following steps: the growth time of the small particles synthesized by the conventional method is shorter than that of the large particles, the crystal order of the crystal structure of the small particles is weaker than that of the large particles, when the crystallinity of the precursor is low, the anode material generated after high-temperature lithiation is correspondingly inherited, and impurity phases can be generated to cause the electrical property degradation of the material, which can influence the performance of the material.
Therefore, the preparation method of the single crystal nickel-cobalt-manganese ternary cathode material still needs to be improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a monocrystal-like nickel cobalt lithium manganate positive electrode material.
The present inventors have proposed based on the following knowledge:
in the prior art, when a single crystal nickel-cobalt-manganese ternary positive electrode material is prepared, the introduction of manganese element mainly has two modes: one is to add the manganese salt as a manganese source. However, when the solid phase method is used, due to the defect of solid phase sintering, the reaction is not complete after sintering due to uneven mixing of various raw materials, so that the material performance is too low; when a liquid-phase raw material synthesis method such as a coprecipitation method is adopted, a manganese source of the liquid-phase raw material usually presents a positive 2-valent ion state in the coprecipitation process, and an induction effect on a precursor crystal structure is lacked, so that an expected effect cannot be achieved if only soluble manganese salts such as manganese nitrate and manganese sulfate are adopted as main elements. And the other is directly adding manganese oxide such as manganese dioxide as a manganese source. When manganese oxide is directly added into the reaction kettle, if the particle size of the manganese oxide is too small, for example, the manganese oxide with nanoparticles is used, the crystal nucleus is too large to exceed the expected index due to the aggregation effect of the nanoparticles, so that a non-target product is synthesized; if the particle size of the manganese oxide is too large, for example, if micron-sized particles are used, although the aggregation effect is not generated, since the particle size of the synthesized target product is in the micron level and the added manganese oxide is used as a core of the primary particles, the micron-sized manganese oxide is much larger than the target product, and thus the micron-sized manganese oxide is not suitable for use as a solid additive. Therefore, the invention takes the manganese oxide as a starting point, and the addition mode of the manganese oxide is improved, so that the invention is provided.
Specifically, the technical scheme provided by the invention is as follows:
a preparation method of a monocrystal-like nickel cobalt lithium manganate positive electrode material comprises the following steps:
the first step is as follows: solution preparation
Preparing soluble metal salts of nickel, cobalt and manganese into a transition metal salt solution;
adding a complexing agent into the prepared transition metal salt solution, or directly preparing a complexing agent solution;
preparing a pH adjusting solution;
the second step is that: preparation of nickel cobalt manganese metal precipitate
Continuously pumping various solutions prepared in the first step into a reaction kettle through different feeding pipes, connecting a reactor filled with manganese salt with a feeding hole of the reaction kettle, introducing protective gas, heating, continuously adding an oxidant into the reactor, reacting, adjusting the flow of the protective gas, bringing manganese oxide generated by the reaction into the reaction kettle, controlling the pH value in the reaction kettle to perform precipitation reaction, and obtaining nickel-cobalt-manganese metal precipitate after the reaction is finished;
the third step: preparation of nickel cobalt manganese precursor
Washing, drying and presintering the nickel-cobalt-manganese metal precipitate to obtain a nickel-cobalt-manganese precursor;
the fourth step: sintering by lithiation
And crushing the nickel-cobalt-manganese precursor, mixing with lithium salt, lithiating and sintering to obtain the monocrystal-like nickel-cobalt-manganese lithium manganate cathode material.
According to the preparation method provided by the invention, manganese salt is decomposed into manganese oxide particles (the main component is manganese dioxide) by adding the oxidant, and the particles are conveyed into the reaction kettle through the protective gas, and the manganese oxides with different particle sizes can be taken away by different protective gas flows, so that more accurate classification of the manganese oxides can be realized by adjusting the flow of the gas; meanwhile, in the transportation process of the manganese oxide, gas is used as a carrier, and a larger distance can be kept between particles, and the distance far exceeds the action distance of the surface energy of the particles, so that the agglomeration of the manganese oxide particles can be avoided; on the other hand, the special crystal structure of manganese dioxide can enable nickel-cobalt-manganese metal ions to generate an ordered layered structure in the precipitation process, so that the degree of order of the material is greatly improved, and a mono-like nickel-cobalt-manganese lithium manganate anode material with excellent comprehensive performance is obtained, thereby completing the invention.
The preparation method of the mono-like lithium nickel cobalt manganese oxide cathode material provided by the embodiment of the invention can further comprise the following additional technical characteristics.
The first step is as follows: solution preparation
Soluble metal salts of nickel, cobalt and manganese are prepared into transition metal salt solution with the total molar concentration of nickel, cobalt and manganese of 1-2 mol/L.
The soluble metal salts of nickel, cobalt and manganese may be nitrates, sulfates, acetates, hydrochlorides, fluorides of nickel, cobalt and manganese, respectively, and hydrates of the salts, etc., and preferably hydrates of the metal salts.
For the use of complexing agents, there are two ways:
the complexing agent can be directly added into the prepared transition metal salt solution, and the adding amount keeps the molar concentration of the complexing agent to be 1-2 mol/L;
or directly preparing 1-2mol/L complexing agent solution.
According to an embodiment of the present invention, the complexing agent is one or a combination of two or more of ammonia, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, ethylenediaminetetraacetic acid (EDTA), ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, succinic acid, citric acid, and malonic acid.
In addition to the complexing agents listed above, other complexing agents commonly used in the art to achieve the same or equivalent technical effects may also be used in the present invention.
In some embodiments, the complexing agent is one of ammonia, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, succinic acid, citric acid, malonic acid.
The two complexing agents can be used according to actual needs. When an alkaline complexing agent such as ammonia is used, the alkaline complexing agent can be prepared independently; when a weakly acidic complexing agent is used, for example ammonium sulfate, it can be added directly to the transition metal salt solution.
In the preparation method provided by the invention, the pH adjusting solution has two supply modes.
Firstly, preparing a regulating solution with the pH value of 13-14 by using inorganic base;
secondly, electrolyte and inorganic base are prepared into adjusting solution with pH value of 13-14.
The inorganic base is one or a composition of more than two of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate and lithium carbonate.
The anion of the electrolyte is the same as the anion of the soluble metal salt of nickel, cobalt and manganese, and the cation of the electrolyte is ammonium ion.
For example, when nickel nitrate hexahydrate, cobalt sulfate heptahydrate, manganese acetate tetrahydrate are employed, then the corresponding electrolytes are ammonium nitrate, ammonium sulfate, and ammonium acetate.
The molar concentration of the anions of the electrolyte is the same as the molar concentration of the anions in the soluble metal salts of nickel, cobalt, manganese described in the first step.
In the invention, the ion concentration in the reaction kettle can be improved by adding the extra electrolyte, and when the precipitation reaction is carried out, the precipitation can be formed at a faster reaction speed, so that the influence of the external environment on the crystallinity of the material is reduced, and the highly ordered nickel-cobalt-manganese precipitate is formed. And the high ion concentration accelerates the precipitation reaction in the solution towards the positive direction, accelerates the precipitation of nickel, cobalt and manganese metal ions, shortens the time of microscale reaction, and simultaneously, because the high ion concentration in the reaction system weakens the influence of pH change on the precipitation reaction, the high ion concentration and the high ion concentration jointly promote the increase of the order degree of the nickel, cobalt and manganese precipitates. Thus, the second provision mode is more preferable.
The second step is that: preparation of nickel cobalt manganese metal precipitate
According to the embodiment provided by the invention, if the complexing agent is added into the transition metal salt solution, the transition metal salt solution added with the complexing agent and the pH adjusting solution are simultaneously and continuously pumped into the three-port reaction kettle through different feeding pipes; if the complexing agent solution is prepared separately, the transition metal salt solution, the complexing agent solution and the pH adjusting solution are continuously pumped into the four-port reaction kettle simultaneously through different feeding pipes.
Preferably, the feeding pipe is arranged at an included angle of 90 degrees with the blades of the reaction kettle at the feeding position in the kettle. The vertical angle between the two enables the direction of the feeding hole force and the direction of the paddle force to be in the same straight line, the utilization efficiency of the material kinetic energy of the feeding hole and the kinetic energy of the paddles can be improved, the sediment can be dispersed most effectively in the stirring and dispersing process, and the consistency of particles is improved.
Meanwhile, preparing another reaction vessel such as a three-neck flask, adding manganese salt, connecting the three-neck flask containing the manganese salt with a feed inlet of a reaction kettle, introducing protective gas, heating, continuously adding an oxidant into the other inlet of the three-neck flask, reacting, adjusting the flow of the protective gas, bringing the manganese oxide generated by the reaction into the reaction kettle, controlling the pH value in the reaction kettle to be 11-13, carrying out precipitation reaction, and obtaining nickel-cobalt-manganese metal precipitate after the reaction is finished.
The manganese oxide particles generated by manganese salt decomposers are conveyed into the reaction kettle through protective gas by controlling the flow of the gas, so that the particles from nanometer to micron in a certain particle size range can be more accurately classified by the transportation of the gas with specific flow, and the agglomeration of the manganese oxide caused by particle stacking is avoided. And the special crystal structure of the manganese dioxide provides a precipitation core for the nickel-cobalt-manganese transition metal precipitate to grow orderly, so that the nickel-cobalt-manganese metal ions generate an ordered layered structure in the precipitation process, and the degree of order of the material is improved. Meanwhile, continuous manganese source enters to bring continuous crystal nucleus, so that primary particles can be kept in a certain range.
According to an embodiment of the present invention, the flow rate of the shielding gas is 1-20mL/min, for example: 1mL/min, 2mL/min, 3mL/min, 4mL/min, 5mL/min, 6mL/min, 7mL/min, 8mL/min, 9mL/min, 10mL/min, 11mL/min, 12mL/min, 13mL/min, 14mL/min, 15mL/min, 16mL/min, 17mL/min, 18mL/min, 19mL/min, 20 mL/min.
The protective gas is one or a composition of more than two of helium, neon, argon, krypton, xenon and nitrogen.
According to the embodiment of the invention, the manganese salt is one or a combination of more than two of manganese nitrate, manganese acetate, manganese oxalate and manganese chloride.
In some embodiments, the manganese salt is one of manganese nitrate, manganese acetate, manganese oxalate, manganese chloride.
The manganese salt may be provided directly as a solid manganese salt or may be provided as an aqueous manganese salt solution. Manganese salts which can be present stably in solid form, preferably with direct addition of manganese salt solids, such as manganese acetate, manganese oxalate, manganese chloride; manganese salts which cannot be present stably in solid form, aqueous solutions of manganese salts, such as manganese nitrate, may be added.
According to the embodiment provided by the invention, the oxidant is one or a composition of more than two of concentrated sulfuric acid, hydrogen peroxide, concentrated nitric acid, potassium permanganate, sodium hypochlorite, sodium percarbonate, sodium perborate, potassium perborate, hydrogen peroxide and ammonium persulfate.
In some embodiments, the oxidizing agent is one of concentrated sulfuric acid, hydrogen peroxide, concentrated nitric acid, potassium permanganate, sodium hypochlorite, sodium percarbonate, sodium perborate, potassium perborate, hydrogen peroxide, ammonium persulfate.
According to an embodiment of the present invention, the amount of the oxidizing agent is 0.1 to 5% by mass of the manganese salt.
In some embodiments, the amount of oxidant used is 1-5% by mass of the manganese salt, for example: 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
The third step: preparation of nickel cobalt manganese precursor
The operations of washing and drying the nickel-cobalt-manganese metal precipitate can be carried out according to the general operation in the field.
Preferably, in the pre-sintering process, decomposable acidic substances are added to sinter together with the dried nickel-cobalt-manganese metal precipitate. The acidic substance is decomposed at high temperature to form acidic gas, so that the grain boundary between primary particles can be corroded, the grain boundary bonding force between the particles is reduced, the primary particles are easier to crush and separate, and uniform single crystal-like primary particles are formed after the primary particles are easier to crush, so that no obvious grain boundary exists in a single particle after the primary particles are crushed, and the compression resistance of the material is improved.
According to the embodiment provided by the invention, the decomposable acidic substance is one or a combination of more than two of ammonium chloride, ammonium acetate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate and ammonium fluoride.
In some embodiments, the decomposable acidic substance is one of ammonium chloride, ammonium acetate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, and ammonium fluoride.
According to the embodiment provided by the invention, the decomposable acidic substance is 0.05-1% of the substance amount of the nickel-cobalt-manganese metal precipitate, such as: 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, etc. When the amount of the additive is too small, the amount of the acidic gas generated by decomposition is too small, and the grain boundaries between the secondary particles cannot be completely corroded, resulting in incomplete crushing in the subsequent step. When the acid substances are excessively added, the generated acid gas is excessive, the pressure of a hearth is easy to be unstable during primary sintering, a non-target product is synthesized, and the nickel-cobalt-manganese precursor is further corroded by the excessive acid gas, so that the product yield is too low
In some embodiments, the decomposable acidic species is 1% of the mass of the nickel cobalt manganese metal precipitate.
According to the embodiment provided by the invention, the temperature of the pre-sintering is 200-: 200 deg.C, 250 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, etc.
According to an embodiment of the present invention, the pre-sintering time is 1-10h, for example: 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, and so forth.
The fourth step: sintering by lithiation
The lithiation sintering may be performed according to procedures common in the art.
According to an embodiment of the present invention, the lithium salt is one or a combination of two or more of lithium carbonate, lithium hydroxide, and lithium acetate.
According to the embodiment provided by the invention, the lithium salt is added in an amount such that the mole number of lithium is 1-1.2 times of the total mole number of nickel, cobalt and manganese in the precursor.
According to an embodiment of the present invention, the temperature of the lithiation sintering is 700-: 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C, etc.
According to an embodiment provided by the present invention, the time of the lithiation sintering is 10 to 24 hours, for example: 10h, 12h, 15h, 18h, 20h, 22h, 24h, etc.
In addition, the term "solution" as used herein means an aqueous solution unless otherwise specifically indicated. For example, the transition metal salt solution refers to an aqueous solution of a transition metal salt, and the complexing agent solution refers to an aqueous solution of a complexing agent; the conditioning solution is a conditioning aqueous solution.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the invention, the ion concentration in the reaction kettle can be improved by adding the extra electrolyte, and when the precipitation reaction is carried out, the precipitation can be formed at a faster reaction speed, so that the influence of the external environment on the crystallinity of the material is reduced, and the highly ordered nickel-cobalt-manganese precipitate is formed. The high ion concentration accelerates the precipitation reaction in the solution towards the positive direction, accelerates the precipitation of nickel, cobalt and manganese metal ions, shortens the time of microscale reaction, and simultaneously, because the high ion concentration in the reaction system weakens the influence of pH change on the precipitation reaction, the high ion concentration and the high ion concentration jointly promote the increase of the order degree of the nickel, cobalt and manganese precipitates.
(2) According to the invention, the manganese oxide particles generated by manganese salt decomposers are conveyed into the reaction kettle through the protective gas by controlling the flow of the gas, so that the nano-sized to micron-sized particles in a certain particle size range can be conveyed into the reaction kettle, the manganese oxide can be classified more accurately by the transportation of the gas with a specific flow velocity and flow rate, and the agglomeration caused by the manganese oxide due to particle stacking is avoided. And the special crystal structure of the manganese dioxide provides a precipitation core for the nickel-cobalt-manganese transition metal precipitate to grow orderly, so that nickel-cobalt-manganese metal ions can generate an ordered layered structure in the precipitation process, and the degree of order of the material is improved. Meanwhile, continuous manganese source enters to bring continuous crystal nucleus, so that primary particles can be kept in a certain range.
(3) In the invention, the feeding position of the feeding pipe in the kettle and the blades of the reaction kettle form an included angle of 90 degrees. The vertical angle between the two enables the direction of the feeding hole force and the direction of the paddle force to be in the same straight line, the utilization efficiency of the material kinetic energy of the feeding hole and the kinetic energy of the paddles can be improved, the most effective dispersion of precipitates in the stirring dispersion process can be achieved, and the particle consistency is improved.
(4) In the invention, decomposable acidic substances are added during the pre-sintering, and the nickel-cobalt-manganese metal precipitate and the dried nickel-cobalt-manganese metal precipitate are sintered together. The acidic substance is decomposed at high temperature to form an acidic atmosphere, so that the grain boundaries among the primary particles can be corroded, the grain boundary bonding force among the particles is reduced, the primary particles are easier to crush and separate, and uniform single crystal-like primary particles are formed after the primary particles are easier to crush, so that no obvious grain boundary exists in a single particle after the primary particles are crushed, and the compression resistance of the material is improved.
(5) The degree of order of the crystal structure of the mono-like nickel cobalt lithium manganate positive electrode material prepared by the method is improved, the mono-like nickel cobalt lithium manganate positive electrode material has a more complete layered structure, the good order of the crystal structure in the subsequent charging and discharging process can ensure that the material has better cyclicity, the more complete layered structure enables the lithium ions to be more easily de-intercalated and de-intercalated, and the cycling stability and the rate capability of the material are improved.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of a quasi-single-crystal nickel cobalt lithium manganate positive electrode material obtained in example 2 and comparative example 1;
FIG. 2 is an SEM image of quasi-single crystal lithium nickel cobalt manganese oxide cathode materials obtained in example 2 and comparative example 2;
FIG. 3 is a graph showing the charge and discharge performance of the quasi-single crystal lithium nickel cobalt manganese oxide positive electrode material obtained in example 2.
Detailed Description
In some embodiments, the preparation method of the mono-like lithium nickel cobalt manganese oxide cathode material comprises the following steps:
the first step is as follows: solution preparation
Preparing soluble metal salts of nickel, cobalt and manganese into a transition metal salt solution with the total molar concentration of nickel, cobalt and manganese of 1-2 mol/L;
adding a complexing agent into the prepared transition metal salt solution to obtain a transition metal salt solution added with the complexing agent;
preparing electrolyte and inorganic base into a regulating solution with the pH value of 13-14;
the second step is that: preparation of nickel cobalt manganese metal precipitate
Continuously pumping various solutions prepared in the first step into a three-port reaction kettle through different feeding pipes simultaneously, and ensuring that the feeding position of the feeding pipe in the kettle and blades of the reaction kettle form an included angle of 90 degrees during feeding; preparing another reaction vessel such as a three-neck flask, adding manganese salt, connecting the three-neck flask containing the manganese salt with a feed inlet of a reaction kettle, introducing protective gas, heating, adding an oxidant into the three-neck flask, reacting, adjusting the flow of the protective gas, bringing manganese oxide generated by the reaction into the reaction kettle, controlling the pH value in the reaction kettle to be 11-13, carrying out precipitation reaction, and obtaining nickel-cobalt-manganese metal precipitate after the reaction is finished;
the third step: preparation of nickel cobalt manganese precursor
Washing and drying the nickel-cobalt-manganese metal precipitate, and adding a decomposable acidic substance for presintering to obtain a nickel-cobalt-manganese precursor;
the fourth step: sintering by lithiation
And crushing the nickel-cobalt-manganese precursor, mixing with lithium salt, lithiating and sintering to obtain the monocrystal-like nickel-cobalt-manganese lithium manganate cathode material.
In other embodiments, the preparation method of the mono-like lithium nickel cobalt manganese oxide cathode material comprises the following steps:
the first step is as follows: solution preparation
Preparing soluble metal salts of nickel, cobalt and manganese into a transition metal salt solution with the total molar concentration of nickel, cobalt and manganese of 1-2 mol/L;
preparing 1-2mol/L complexing agent solution;
preparing electrolyte and inorganic base into a regulating solution with the pH value of 13-14;
the second step is that: preparation of nickel cobalt manganese metal precipitate
Continuously pumping various solutions prepared in the first step into four reaction kettles through different feeding pipes simultaneously, and ensuring that the feeding position of the feeding pipe in the kettle and blades of the reaction kettle form an included angle of 90 degrees during feeding; preparing another reaction vessel such as a three-neck flask, adding manganese salt, connecting the three-neck flask containing the manganese salt with a feed inlet of a reaction kettle, introducing protective gas, heating, adding an oxidant into the three-neck flask, reacting, adjusting the flow of the protective gas, bringing manganese oxide generated by the reaction into the reaction kettle, controlling the pH value in the reaction kettle to be 11-13, carrying out precipitation reaction, and obtaining nickel-cobalt-manganese metal precipitate after the reaction is finished;
the third step: preparation of nickel cobalt manganese precursor
Washing and drying the nickel-cobalt-manganese metal precipitate, and adding a decomposable acidic substance for presintering to obtain a nickel-cobalt-manganese precursor;
the fourth step: sintering by lithiation
And crushing the nickel-cobalt-manganese precursor, mixing with lithium salt, lithiating and sintering to obtain the monocrystal-like nickel-cobalt-manganese lithium manganate cathode material.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Examples 1 to 4
The guard gas flow rate was different in the second step in examples 1 to 4, and the other operation steps were the same. Example 1 guard flow rate was 1mL/min, example 2 guard flow rate was 5mL/min, example 3 guard flow rate was 10mL/min, and example 4 guard flow rate was 20mL/min, as shown in Table 1.
The specific experimental operations in each example were:
the first step is as follows: solution preparation
Weighing 9.6mol of nickel nitrate hexahydrate, 0.2mol of cobalt acetate tetrahydrate and 0.2mol of manganese sulfate monohydrate, adding into a container, and adding a proper amount of water to enable the total volume of the solution to be 5L, thereby obtaining a salt solution with the total concentration of transition metals being 2 mol/L;
weighing 5mol of ammonium sulfate as a complexing agent, and adding the ammonium sulfate into the prepared salt solution to obtain a transition metal salt solution added with the complexing agent;
weighing 19.2mol of ammonium nitrate, 0.4mol of ammonium acetate and 0.2mol of ammonium sulfate, adding into a beaker, adding deionized water to make the total volume of the solution be 5L, and adding a proper amount of sodium hydroxide to prepare an adjusting solution with the pH value of 13.5.
The second step is that: preparation of nickel cobalt manganese metal precipitate
Continuously pumping the transition metal salt solution added with the complexing agent and the pH value adjusting solution prepared in the first step into a three-port reaction kettle simultaneously through a feeding pipe, wherein the feeding position of the feeding pipe in the kettle and the blades of the reaction kettle form an included angle of 90 degrees during feeding; preparing a three-neck flask, adding 20g of manganese acetate, connecting the three-neck flask filled with the manganese acetate with a feed inlet of a reaction kettle, introducing nitrogen, heating to keep the temperature in the three-neck flask at 220 ℃, adding 1g of potassium permanganate serving as an oxidant into the three-neck flask, reacting, adjusting the flow of protective gas nitrogen, introducing nitrogen to bring 3g (mainly manganese dioxide) of manganese oxide generated by the reaction into the reaction kettle, controlling the pH value in the reaction kettle to be 11.5, carrying out a precipitation reaction, and obtaining nickel-cobalt-manganese metal precipitate after the reaction is finished.
The third step: preparation of nickel cobalt manganese precursor
And washing and drying the nickel-cobalt-manganese metal precipitate, adding 0.5g of ammonium carbonate and 0.5g of ammonium nitrate into 100g of the washed and dried nickel-cobalt-manganese metal precipitate, uniformly mixing, and presintering at 450 ℃ for 5 hours to obtain a nickel-cobalt-manganese precursor.
The fourth step: sintering by lithiation
And crushing the nickel-cobalt-manganese precursor in the last step to obtain a crushed nickel-cobalt-manganese precursor, weighing 50g of the crushed nickel-cobalt-manganese precursor, performing ICP-OES detection and analysis, wherein the total molar weight of nickel, cobalt and manganese metal ions is 0.54mol, weighing 0.57mol of lithium hydroxide, mixing, and performing lithiation at the high temperature of 730 ℃ for 12 hours to obtain the monocrystal-like nickel-cobalt-manganese acid lithium positive electrode material.
Comparative example 1
The first step is as follows: solution preparation
Weighing 9.6mol of nickel nitrate hexahydrate, 0.2mol of cobalt acetate tetrahydrate and 0.2mol of manganese sulfate monohydrate, adding into a container, and adding a proper amount of water to enable the total volume of the solution to be 5L, thereby obtaining a salt solution with the total concentration of transition metals being 2 mol/L;
weighing 5mol of ammonium sulfate as a complexing agent, and adding the ammonium sulfate into the prepared salt solution to obtain a transition metal salt solution added with the complexing agent;
weighing 19.2mol of ammonium nitrate, 0.4mol of ammonium acetate and 0.2mol of ammonium sulfate, adding into a beaker, adding deionized water to make the total volume of the solution be 5L, and adding a proper amount of sodium hydroxide to prepare an adjusting solution with the pH value of 13.5.
The second step is that: preparation of nickel cobalt manganese metal precipitate
Continuously pumping the solution prepared in the first step into a three-port reaction kettle through a feeding pipe at the same time, and ensuring that the feeding position of the feeding pipe in the kettle and blades of the reaction kettle form an included angle of 90 degrees during feeding; preparing a three-neck flask of a reaction vessel, directly and continuously adding 3g of manganese dioxide through a feed inlet of the reaction kettle, controlling the pH value in the reaction kettle to be 11.5, carrying out precipitation reaction, and obtaining nickel-cobalt-manganese metal precipitate after the reaction is finished.
The third step: preparation of nickel cobalt manganese precursor
And washing and drying the nickel-cobalt-manganese metal precipitate, adding 0.5g of ammonium carbonate and 0.5g of ammonium nitrate into 100g of the washed and dried nickel-cobalt-manganese metal precipitate, uniformly mixing, and presintering at 450 ℃ for 5 hours to obtain a nickel-cobalt-manganese precursor.
The fourth step: sintering by lithiation
And crushing the nickel-cobalt-manganese precursor in the last step to obtain a crushed nickel-cobalt-manganese precursor, weighing 50g of the crushed nickel-cobalt-manganese precursor, performing ICP-OES detection and analysis, wherein the total molar weight of nickel, cobalt and manganese metal ions is 0.54mol, weighing 0.57mol of lithium hydroxide, mixing, and performing lithiation at the high temperature of 730 ℃ for 12 hours to obtain the monocrystal-like nickel-cobalt-manganese acid lithium positive electrode material.
Comparative example 2
The first step is as follows: solution preparation
Weighing 9.6mol of nickel nitrate hexahydrate, 0.2mol of cobalt acetate tetrahydrate and 0.2mol of manganese sulfate monohydrate, adding into a container, and adding a proper amount of water to enable the total volume of the solution to be 5L, thereby obtaining a salt solution with the total concentration of transition metals being 2 mol/L;
weighing 5mol of ammonium sulfate as a complexing agent, and adding the ammonium sulfate into the prepared salt solution to obtain a transition metal salt solution added with the complexing agent;
weighing 19.2mol of ammonium nitrate, 0.4mol of ammonium acetate and 0.2mol of ammonium sulfate, adding into a beaker, adding deionized water to make the total volume of the solution be 5L, and adding a proper amount of sodium hydroxide to prepare an adjusting solution with the pH value of 13.5;
the second step is that: preparation of nickel cobalt manganese metal precipitate
Continuously pumping the solution prepared in the first step into a three-port reaction kettle through a feeding pipe at the same time, and ensuring that the feeding position of the feeding pipe in the kettle and blades of the reaction kettle form an included angle of 90 degrees during feeding; preparing a three-neck flask of a reaction container, adding 20g of manganese acetate, connecting the three-neck flask containing the manganese acetate with a feed inlet of a reaction kettle, introducing nitrogen, heating to keep the temperature in the three-neck flask at 220 ℃, adding 1g of potassium permanganate serving as an oxidant into the three-neck flask, reacting, adjusting the flow of protective gas to be 5mL/min, introducing the nitrogen to bring manganese oxide generated by the reaction into the reaction kettle, controlling the pH value in the reaction kettle to be 11.5, carrying out precipitation reaction, and obtaining nickel-cobalt-manganese metal precipitate after the reaction is finished;
the third step: preparation of nickel cobalt manganese precursor
And (3) washing and drying the nickel-cobalt-manganese metal precipitate, and presintering 100g of the washed and dried nickel-cobalt-manganese metal precipitate at 450 ℃ for 5h to obtain a nickel-cobalt-manganese precursor.
The fourth step: sintering by lithiation
And crushing the nickel-cobalt-manganese precursor in the last step to obtain a crushed nickel-cobalt-manganese precursor, weighing 50g of the crushed nickel-cobalt-manganese precursor, performing ICP-OES detection and analysis, wherein the total molar weight of nickel, cobalt and manganese metal ions is 0.54mol, weighing 0.57mol of lithium hydroxide, mixing, and performing lithiation at the high temperature of 730 ℃ for 12 hours to obtain the monocrystal-like nickel-cobalt-manganese acid lithium positive electrode material.
Comparative example 3
The first step is as follows: solution preparation
Weighing 9.6mol of nickel nitrate hexahydrate, 0.2mol of cobalt acetate tetrahydrate and 0.2mol of manganese sulfate monohydrate, adding into a container, and adding a proper amount of water to enable the total volume of the solution to be 5L, thereby obtaining a salt solution with the total concentration of transition metals being 2 mol/L;
weighing 5mol of ammonium sulfate as a complexing agent, and adding the ammonium sulfate into the prepared salt solution to obtain a transition metal salt solution added with the complexing agent;
weighing 19.2mol of ammonium nitrate, 0.4mol of ammonium acetate and 0.2mol of ammonium sulfate, adding into a beaker, adding deionized water to make the total volume of the solution be 5L, and adding a proper amount of sodium hydroxide to prepare an adjusting solution with the pH value of 13.5;
the second step is that: preparation of nickel cobalt manganese metal precipitate
Continuously pumping the solution prepared in the first step into a three-port reaction kettle through a feeding pipe at the same time, and ensuring that the feeding position of the feeding pipe in the kettle and blades of the reaction kettle form an included angle of 90 degrees during feeding; preparing a three-neck flask of a reaction vessel, adding 20g of manganese acetate, connecting the three-neck flask containing the manganese acetate with a feed inlet of a reaction kettle, introducing nitrogen, heating to keep the temperature in the three-neck flask at 220 ℃, adding 1g of potassium permanganate serving as an oxidant into the three-neck flask, reacting, adjusting the flow of protective gas to be 0.5mL/min, introducing the nitrogen to bring manganese oxide generated by the reaction into the reaction kettle, controlling the pH value in the reaction kettle to be 11.5, carrying out a precipitation reaction, and obtaining nickel-cobalt-manganese metal precipitate after the reaction is finished.
The third step: preparation of nickel cobalt manganese precursor
And washing and drying the nickel-cobalt-manganese metal precipitate, adding 0.5g of ammonium carbonate and 0.5g of ammonium nitrate into 100g of the washed and dried nickel-cobalt-manganese metal precipitate, uniformly mixing, and presintering at 450 ℃ for 5 hours to obtain a nickel-cobalt-manganese precursor.
The fourth step: sintering by lithiation
And crushing the nickel-cobalt-manganese precursor in the last step to obtain a crushed nickel-cobalt-manganese precursor, weighing 50g of the crushed nickel-cobalt-manganese precursor, performing ICP-OES detection and analysis, wherein the total molar weight of nickel, cobalt and manganese metal ions is 0.54mol, weighing 0.57mol of lithium hydroxide, mixing, and performing lithiation at the high temperature of 730 ℃ for 12 hours to obtain the monocrystal-like nickel-cobalt-manganese acid lithium positive electrode material.
Performance testing
1. XRD characterization: the crystal structure of the prepared sample is characterized by using an X-ray diffractometer of D8 advanced model manufactured by Brucker company in Germany, the tube voltage is 40kV, the tube current is 40mA, and the scanning range is 10-70 degrees.
2. And (4) SEM characterization: the microscopic morphology of the powder was observed by SEM at an operating voltage of 20 kV.
3. And (3) electrical property characterization: the positive pole piece is composed of an active material (a monocrystal-like nickel cobalt lithium manganate positive pole material), acetylene black and PVDF (the mass ratio is 9:0.5: 0.5). The cathode slurry was coated on a current collector Al foil at a density of 3 mg/cm 2. A CR2025 button cell was assembled in a glove box under Ar atmosphere using lithium metal as a negative electrode, an electrolyte was a 1 mol/L LiPF6 solution, and a solvent was a DMC: EMC: EC (volume ratio: 1:1) mixed solution.
TABLE 1 comparison of specific capacities of button cells assembled in examples 1-4 and comparative examples 1-3
As can be seen from Table 1, in examples 1-4, the flow rate of the carrier gas is in a suitable interval, and the quantity and the size of the oxides of manganese capable of being brought into the reaction kettle are in the interval range, so that the prepared single-crystal lithium nickel cobalt manganese oxide cathode material has good performance. Particularly, in example 2, since the carrier gas flow rate is matched with each parameter of the reaction system, the superior effect is generated, and the constant pressure ratio (1-Q1/Q) and the first effect F/Q are both superior to those of other examples. In comparative example 3, the flow rate of the guard gas was 0.5mL/min, and too small a flow rate of the guard gas did not contribute to the transport of the particulate manganese oxide, and most of the particles settled by their own weight during the transport and did not contribute to the reaction in the reactor. The resulting positive electrode material has poor electrical properties.
Comparative example 1, manganese dioxide is directly added, the charge-discharge capacity, the first effect and the constant voltage ratio of the obtained cathode material are not superior to those of the embodiment of the invention, mainly because solid manganese dioxide particles cause agglomeration, so that manganese dioxide is invalid, and because the carrier of manganese dioxide is protective gas, the agglomeration of the particles is avoided, and the prepared monocrystal nickel-cobalt-manganese cathode material has better electrical property.
Comparative example 2 is mainly to add no low-temperature decomposed acidic substance in the pre-sintering step, thus resulting in incomplete crushing upon crushing, resulting in excessive particles, resulting in incomplete sintering coating, resulting in reduced electrical properties.
FIG. 1: example 2 in comparison with the nickel-cobalt-manganese precursor xrd synthesized in comparative example 1, by controlling the flow rate of the gas so that nano-to micron-sized particles in a suitable particle size range are transported into the reaction vessel by the shielding gas, the transport of the gas enables more precise classification, and the particle stacking brings about the agglomeration of manganese dioxide particles. The special crystal structure of the manganese dioxide can enable nickel, cobalt and manganese metal ions to generate an ordered layered structure in the precipitation process, and the degree of order of the material is improved. Xrd spectrum therefore shows that the crystallinity of example 2 is higher than that of comparative example 1
FIG. 2: in example 2 and comparative example 2, since the acidic decomposed substance was not added during the pre-sintering, the grain boundary thereof was not corroded during the pre-sintering, resulting in difficulty in separation thereof in the subsequent crushing step. Therefore, after example 2 and comparative example 2 were crushed, the degree of crushing of example 2 was better than that of comparative example 2.
FIG. 3: 0.1C discharge diagram of the single crystal nickel cobalt manganese cathode material prepared in example 2. The 0.1C charging capacity is 226.12mAh/g, the 0.1C discharging capacity is 225.14/mAh/g, the first effect is 99.57%, and the comprehensive performance is better.
The invention is illustrated by the above examples to describe the preparation method of the mono-like lithium nickel cobalt manganese oxide cathode material of the invention, but the invention is not limited to the above examples, that is, the invention is not limited to the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a monocrystal-like nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps:
the first step is as follows: solution preparation
Preparing soluble metal salts of nickel, cobalt and manganese into a transition metal salt solution;
adding a complexing agent into the prepared transition metal salt solution, or directly preparing a complexing agent solution;
preparing a pH adjusting solution;
the second step is that: preparation of nickel cobalt manganese metal precipitate
Continuously pumping various solutions prepared in the first step into a reaction kettle through different feeding pipes, connecting a reactor filled with manganese salt with a feeding hole of the reaction kettle, introducing protective gas, heating, continuously adding an oxidant into the reactor, reacting to generate manganese oxide, adjusting the flow of the protective gas, bringing the manganese oxide generated by the reaction into the reaction kettle, enabling the flow of the protective gas to be 1-20mL/min so as to realize more accurate classification of the manganese oxide, avoiding agglomeration caused by the manganese oxide due to particle stacking, controlling the pH value in the reaction kettle to perform a precipitation reaction, and obtaining a nickel-cobalt-manganese metal precipitate after the reaction is finished;
the third step: preparation of nickel cobalt manganese precursor
Washing, drying and presintering the nickel-cobalt-manganese metal precipitate to obtain a nickel-cobalt-manganese precursor;
the fourth step: sintering by lithiation
And crushing the nickel-cobalt-manganese precursor, mixing with lithium salt, lithiating and sintering to obtain the monocrystal-like nickel-cobalt-manganese lithium manganate cathode material.
2. The method for preparing a single-crystal-like lithium nickel cobalt manganese oxide positive electrode material of claim 1, wherein in the first step, the total molar concentration of nickel, cobalt and manganese in the transition metal salt solution is 1-2 mol/L.
3. The method for preparing a mono-like lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein when the complexing agent is added into the transition metal salt solution, the adding amount of the complexing agent is that the molar concentration of the complexing agent is kept to be 1-2 mol/L; when the complexing agent solution is directly prepared, the molar concentration of the complexing agent in the solution is 1-2 mol/L; the complexing agent is one or a composition of more than two of ammonia water, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, succinic acid, citric acid and malonic acid.
4. The method for preparing a single-crystal-like lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein the preparing the pH adjusting solution comprises: preparing an electrolyte and an inorganic base into a regulating solution with the pH value of 13-14, wherein the anion of the electrolyte is the same as the anion in the soluble metal salt of nickel, cobalt and manganese in the first step, the molar concentration of the anion of the electrolyte is the same as the molar concentration of the anion in the soluble metal salt of nickel, cobalt and manganese in the first step, and the cation of the electrolyte is ammonium ion; the inorganic base is one or a composition of more than two of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate and lithium carbonate.
5. The method for preparing a mono-like lithium nickel cobalt manganese oxide positive electrode material of claim 1, wherein in the second step, the manganese salt is one or a combination of more than two of manganese nitrate, manganese acetate, manganese oxalate and manganese chloride; the oxidant is one or a composition of more than two of concentrated sulfuric acid, hydrogen peroxide, concentrated nitric acid, potassium permanganate, sodium hypochlorite, sodium percarbonate, sodium perborate, potassium perborate and ammonium persulfate; the dosage of the oxidant is 0.1-5% of the mass of the manganese salt.
6. The method for preparing a mono-like lithium nickel cobalt manganese oxide cathode material of claim 1, wherein in the second step, the feeding pipe is at an angle of 90 ° with the paddle of the reaction kettle at the feeding position in the kettle.
7. The method for preparing a mono-like lithium nickel cobalt manganese oxide cathode material according to claim 1, wherein in the second step, the pH value in the reaction kettle is controlled to be 11-13.
8. The method for preparing a mono-like lithium nickel cobalt manganese oxide positive electrode material of claim 1, wherein in the third step, a decomposable acidic substance is added during the pre-sintering, and the decomposable acidic substance is one or a combination of more than two of ammonium chloride, ammonium acetate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate and ammonium fluoride; the decomposable acidic substance is 0.05-1% of the mass of the nickel-cobalt-manganese metal precipitate.
9. The method for preparing the mono-like lithium nickel cobalt manganese oxide cathode material as claimed in claim 1, wherein the pre-sintering temperature is 200-500 ℃ and the time is 1-10 h.
10. The mono-like nickel cobalt lithium manganate positive electrode material obtained by the preparation method of any one of claims 1 to 9.
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