CN115353154B - Solid-state lithium ion battery anode material precursor and preparation method thereof - Google Patents
Solid-state lithium ion battery anode material precursor and preparation method thereof Download PDFInfo
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Abstract
Solid-state lithium ion battery anode material precursor with chemical formula of Ni x Co y Mn z M k (OH) 2 X is more than or equal to 0.8 and less than 1, y is more than or equal to 0 and less than 0.2, z is more than or equal to 0 and less than or equal to 0.004, and x+y+z+k=1. Comprising the following steps: 1. preparing a metal mixed solution of Ni, co, mn, M; preparing a precipitator and a complexing agent; 2. adding a precipitator, a complexing agent and a fast ion conductor into a kettle to prepare a base solution, controlling the pH value of the base solution to be 12.60-12.80 and the temperature to be 40-60 ℃; 3. continuously adding the metal mixed solution, the precipitant and the complexing agent into a kettle at the flow rate of 50-300 mL/min for coprecipitation, and stopping liquid feeding when the particles grow to the target granularity; overflowing the kettle to a concentration device, wherein the concentration of a complexing agent in slurry in the kettle is 0.25-0.35 mol/L, and the density of the slurry is kept to be 1.40-1.60; 4. and centrifuging, washing and drying the coprecipitation product to obtain a solid-state lithium ion battery anode material precursor. The precursor is of a compact structure, so that the internal impedance of the positive electrode material can be reduced, and the electrochemical performance can be improved.
Description
Technical Field
The invention relates to the field of battery anode materials, in particular to a solid-state lithium ion battery anode material precursor and a preparation method thereof.
Background
Compared with a lithium ion battery using electrolyte as an ionic conduction agent, the solid-state battery has the advantages of high safety, high energy density, strong cycle performance and the like, and has very broad prospects.
However, the solid-state battery mainly uses a solid electrolyte as an ion conductive agent, and since the effective contact between an electrode and the solid electrolyte is weak, the transmission kinetics of ions in a solid substance is low, so that the solid-state battery is required to be compact in the inside for a positive electrode material, thereby facilitating the transmission of lithium ions in the charge and discharge processes. When preparing a solid lithium ion battery positive electrode material precursor by a coprecipitation method, the initial granularity is difficult to be reduced, so that pores are formed in a final product, the diffusion of lithium ions is influenced, the internal impedance of the positive electrode material is overlarge, and the electrical property of the positive electrode material is reduced.
Therefore, how to prepare an internally compact ternary precursor to effectively solve the above problems is the problem to be solved by the present invention.
Disclosure of Invention
The invention aims to provide a solid-state lithium ion battery anode material precursor and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
solid-state lithium ion battery anode material precursor with chemical formula of Ni x Co y Mn z M k (OH) 2 Wherein M is one or more of Zr, al and B, x is more than or equal to 0.8 and less than 1, y is more than or equal to 0 and less than 0.2, z is more than or equal to 0 and less than or equal to 0.2, k is more than or equal to 0 and less than or equal to 0.004, and x+y+z+k=1.
The relevant content explanation in the technical scheme is as follows:
1. in the scheme, the D50 is 2.4-2.9 um, and the tap density is 1.85-2.3 g/cm 3 The granularity diameter is 0.6 < (D90-D10)/D50 < 0.9, the thickness of primary particles is 200-400 nm, the length of primary particles is 400-800 nm, the internal structure is compact, and the specific surface area is 2-8 m 2 /g。
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the solid-state lithium ion battery anode material precursor comprises the following steps:
step one, preparing a metal mixed solution of Ni, co, mn, M;
preparing sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-10 mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 1.5-3.5 mol/L as a complexing agent;
step two, adding the precipitant, the complexing agent and the fast ion conductor into a closed synthesis kettle with the effective volume of 100-300L to prepare a base solution, controlling the pH value of the base solution to be 12.60-12.80 through the precipitant, and maintaining the temperature at 40-60 ℃;
step three, keeping a synthesis kettle stirring and opening, continuously adding the metal mixed solution, the precipitant and the complexing agent in the step one into the synthesis kettle at the flow rate of 50-300 mL/min respectively for coprecipitation reaction, and stopping liquid feeding when particles grow to the target particle size;
the overflow liquid of the reaction kettle flows to the concentration equipment, the pH value in the reaction process is maintained at 12.00-12.40, the reaction temperature is maintained at 40-60 ℃, the rotating speed of the reaction kettle is 650-850 r/min, the concentration of the complexing agent in the slurry in the reaction kettle is 0.25-0.35 mol/L, and the density of the slurry in the reaction kettle is maintained at 1.40-1.60;
and fourthly, centrifuging, washing and drying the coprecipitation product obtained in the third step to obtain a solid-state lithium ion battery anode material precursor.
The relevant content explanation in the technical scheme is as follows:
1. in the above scheme, the target granularity in the third step is 2.4-2.9 um.
2. In a further technical scheme, in the first step, the total molar concentration of Ni, co, mn, M is 1.7-2.3 mol/L.
3. In a further technical scheme, in the second step, the ammonia concentration in the base solution is 0.15-0.25 mol/L.
4. In a further technical scheme, in the second step, the fast ion conductor is Li 3 PO 4 、Li 7 La 3 Zr 2 O 12 One or two of them.
5. In a further technical scheme, in the second step, the concentration of the fast ion conductor in the base solution is 3-6 g/L, and the granularity D50 is 100-300 nm.
The working principle and the advantages of the invention are as follows:
1. according to the invention, a fast ion conductor with a certain concentration is added into a base solution, and then a coprecipitation method is adopted to prepare a solid-state lithium ion battery anode material precursor with a compact structure. Because the particle size D50 of the fast ion conductor is smaller, the fast ion conductor easily enters the pores in the precursor in the growth process, and plays a role in filling the pores, so that the precursor is more compact in the inside. In addition, the fast ion conductor has the capability of ion transmission, can provide a bridge for lithium ion transmission among pores, and plays a role in reducing impedance. The particle size D50 of the fast ion conductor added in the base solution is preferably 100-300 nm, the concentration is 3-6 g/L, if the particle size D50 is too small, the fast ion conductor can fall off in the filling process, and if the particle size D50 is too large, part of smaller pores can not be filled. Too low a concentration of the fast ion conductor may result in incomplete pore filling, and too high a concentration may result in reduced capacity because the fast ion conductor is not electrochemically active.
2. According to the invention, the M element is introduced into the metal mixed solution, so that the doping at the atomic level is realized, the uniformity of the doped element is improved, the introduction of the M element is beneficial to widening the transmission channel of lithium ions, and the transmission efficiency of the lithium ions is improved.
3. The invention obtains the D50 of 2.4-2.9 um and the tap density of 1.85-2.3 g/cm by regulating and controlling the reaction process conditions of the coprecipitation stage 3 The diameter distance of the granularity is 0.6 < (D90-D10)/D50 is less than 0.9, the thickness of the primary particles is 200-400 nm, the length of the primary particles is 400-800 nm, and the specific surface area is 2-8 m 2 And/g is a solid lithium ion battery anode material precursor with a compact structure.
4. The preparation method has the advantages of reliable process, simplicity, easy operation and easy industrial production.
In summary, the invention prepares the solid-state lithium ion battery anode material precursor with compact structure inside by adding the fast ion conductor with certain concentration into the base solution and adopting the coprecipitation method, and the structure can reduce the internal impedance of the anode material, thereby improving the electrochemical performance.
Drawings
FIG. 1 is an SEM image of a precursor prepared according to an embodiment of the present invention;
FIG. 2 is a cross-sectional view of a precursor prepared according to an embodiment of the present invention;
FIG. 3 is a cross-sectional view of a precursor prepared in comparative example 1 of the present invention;
FIG. 4 is a cross-sectional view of a precursor prepared in comparative example 3 of the present invention;
FIG. 5 is a cross-sectional view of a precursor prepared in comparative example 4 of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples:
the present invention will be described in detail with reference to the drawings, wherein modifications and variations are possible in light of the teachings of the present invention, without departing from the spirit and scope of the present invention, as will be apparent to those of skill in the art upon understanding the embodiments of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure.
The term (terms) as used herein generally has the ordinary meaning of each term as used in this field, in this disclosure, and in the special context, unless otherwise noted. Certain terms used to describe the present disclosure are discussed below, or elsewhere in this specification, to provide additional guidance to those skilled in the art in connection with the description herein.
Examples:
a preparation method of a solid-state lithium ion battery anode material precursor comprises the following steps:
preparing a metal mixed solution of Ni, co, mn, zr, wherein the molar ratio of Ni, co, mn, zr elements is 85:10:4.8:0.2, and the total molar concentration of Ni, co, mn and Zr is 2mol/L.
Sodium hydroxide or potassium hydroxide solution with the molar concentration of 10mol/L is prepared as a precipitator.
Preparing ammonia water solution with the molar concentration of 2mol/L as a complexing agent.
Step two, adding the precipitant, the complexing agent and the fast ion conductor Li into a closed synthesis kettle with the effective volume of 100L 3 PO 4 Preparing a base solution, controlling the pH value of the base solution to be 12.60-12.80 through a precipitator, and maintaining the temperature at 50 ℃ and the ammonia concentration in the base solution to be 0.25mol/L; fast ion conductor Li in the base solution 3 PO 4 The concentration of (C) was 4g/L and the particle size D50 was 200nm.
And step three, keeping the synthesis kettle stirring open, continuously adding the metal mixed solution, the precipitant and the complexing agent in the step one into the synthesis kettle at the flow rate of 50-300 mL/min respectively for coprecipitation reaction, and stopping liquid feeding when the metal mixed solution grows to the target granularity.
The overflow liquid of the reaction kettle flows to the concentration equipment, the pH value in the reaction process is maintained at 12.00-12.40, the reaction temperature is maintained at 50 ℃, the rotating speed of the reaction kettle is 800r/min, the concentration of the complexing agent in the slurry in the reaction kettle is 0.25mol/L, and the density of the slurry in the reaction kettle is maintained at 1.40-1.60.
Step four, centrifuging, washing and drying the coprecipitation product in the step three to obtain a solid lithium ion battery anode material precursor, wherein the chemical formula of the precursor is Ni 0.85 Co 0.10 Mn 0.048 Zr 0.002 (OH) 2 The D50 is 2.832um, the tap density is 1.98g/cm 3 The granularity diameter distance is 0.789, the thickness of primary particles is 200-400 nm, the length of primary particles is 400-800 nm, and the specific surface area is 5.68m 2 And/g, the relevant data are shown in Table 1.
Comparative example 1:
unlike the embodiment, the fast ion conductor Li in the second step 3 PO 4 The concentration was different, and the fast ion conductor Li was not added in this comparative example 1 3 PO 4 The remainder are identical to the examples. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 2:
unlike the embodiment, the fast ion conductor Li in the second step 3 PO 4 Concentration is different, in this comparative example 2, the fast ion conductor Li 3 PO 4 The concentration was 8g/L, and the rest was the same as in the examples. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 3:
unlike the embodiment, the fast ion conductor Li in the second step 3 PO 4 The particle size D50 is different, and the fast ion conductor Li in this comparative example 3 3 PO 4 The particle size D50 was 50nm, the remainder being exactly the same as in the examples. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 4:
unlike the embodiment, the fast ion conductor Li in the second step 3 PO 4 The particle size D50 is different, and the fast ion conductor Li in this comparative example 4 3 PO 4 The particle size D50 was 400nm, the remainder being exactly the same as in the examples. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 5:
the difference from the examples is that the ratio of Zr element in the first step is different, zr is not added in the comparative example 5, and the rest is the same as the examples. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Table 1 correlation test data for products obtained in each example
Comparing the data of each example in table 1, it can be seen that: fast ion conductor Li 3 PO 4 The concentration and the granularity D50 of the precursor product have no obvious influence on the granularity D50 and the diameter distance of the precursor product, and have important influence on the tap density, the specific surface area of the precursor product, the resistivity and the first discharge capacity of the corresponding positive electrode material. Along with the fast ion conductor Li 3 PO 4 The increase of the concentration of the precursor product increases the tap density, decreases the specific surface area, and indicates that the porosity in the product is decreasing, the resistivity of the corresponding positive electrode material is decreasing, and the phenomenon that the discharge capacity is increasing and then decreasing occurs for the first time. This is due to the fast ion conductor Li 3 PO 4 The electrochemical activity is not generated, and the content of the positive electrode material is reduced by increasing the concentration, so that the capacity is reduced. In addition, when the fast ion conductor Li 3 PO 4 When the particle size D50 of the positive electrode material is not in the range of 100 to 300nm, the internal pores of the corresponding positive electrode material increase, and the specific resistance becomes large, resulting in a decrease in the first discharge capacity. As can be seen from comparative example 5, doping of Zr element can obviously widen the transmission channel of lithium ions and improve the first discharge capacity.
FIGS. 1 to 5 are respectively a field emission electron microscope image and a cross-sectional electron microscope image of the products prepared in examples, comparative example 1, comparative example 3 and comparative example 4, and it can be seen from FIG. 2 that when the concentration of the fast ion conductor in the base solution is 4g/L and the particle size D50 is 200nm, the cross section thereof shows a smooth and nonporous shape, forming an inner dense structure, the thickness of the outer primary particles is 200 to 400nm, and the length of the primary particles is 400 to 800nm.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (4)
1. A preparation method of a solid-state lithium ion battery anode material precursor is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing a metal mixed solution of Ni, co, mn, M;
preparing sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-10 mol/L as a precipitant;
preparing an ammonia water solution with the molar concentration of 1.5-3.5 mol/L as a complexing agent;
adding the precipitant, the complexing agent and the fast ion conductor into a closed reaction kettle with the effective volume of 100-300L to prepare a base solution, controlling the pH value of the base solution to be 12.60-12.80 through the precipitant, and maintaining the temperature at 40-60 ℃;
the fast ion conductor is Li 3 PO 4 、Li 7 La 3 Zr 2 O 12 One or two of them;
the concentration of the fast ion conductor in the base solution is 3-6 g/L, and the granularity D50 of the fast ion conductor is 100-300 nm;
step three, keeping a reaction kettle stirring and opening, continuously adding the metal mixed solution, the precipitant and the complexing agent in the step one into the reaction kettle at the flow rate of 50-300 mL/min respectively for coprecipitation reaction, and stopping liquid feeding when particles grow to the target particle size;
the overflow liquid of the reaction kettle flows to the concentration equipment, the pH value in the reaction process is maintained at 12.00-12.40, the reaction temperature is maintained at 40-60 ℃, the rotating speed of the reaction kettle is 650-850 r/min, the concentration of a complexing agent in slurry in the reaction kettle is 0.25-0.35 mol/L, and the density of the slurry in the reaction kettle is maintained at 1.40-1.60;
step four, centrifuging, washing and drying the coprecipitation product obtained in the step three to obtain a solid-state lithium ion battery anode material precursor;
the chemical formula of the precursor is Ni x Co y Mn z M k (OH) 2 Wherein M is one or more of Zr, al and B, x is more than or equal to 0.8 and less than 1, y is more than or equal to 0 and less than 0.2, z is more than or equal to 0 and less than or equal to 0.2, k is more than or equal to 0 and less than or equal to 0.004, and x+y+z+k=1.
2. The method of manufacturing according to claim 1, characterized in that: in the first step, the total molar concentration of Ni, co, mn, M is 1.7-2.3 mol/L.
3. The method of manufacturing according to claim 1, characterized in that: in the second step, the ammonia concentration in the base solution is 0.15-0.25 mol/L.
4. The method of manufacturing according to claim 1, characterized in that: the D50 of the precursor is 2.4-2.9 mu m, and the tap density is 1.85-2.3 g/cm 3 The particle size diameter is 0.6 < (D90-D10)/D50 < 0.9, the thickness of primary particles is 200-400 nm, the length of primary particles is 400-800 nm, and the specific surface area is 2-8 m 2 /g。
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