CN113292114A - Preparation method of Ti-Mg-containing co-doped NCM811 type precursor - Google Patents

Preparation method of Ti-Mg-containing co-doped NCM811 type precursor Download PDF

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CN113292114A
CN113292114A CN202110563658.3A CN202110563658A CN113292114A CN 113292114 A CN113292114 A CN 113292114A CN 202110563658 A CN202110563658 A CN 202110563658A CN 113292114 A CN113292114 A CN 113292114A
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罗学涛
李岩
黄柳青
陈广玉
丁和磊
索佳苗
张嘉韵
瞿心卓
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Xiamen University
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a Ti and Mg-containing co-doped high-nickel ternary precursor, which comprises the following steps: firstly, mixing nickel-cobalt-manganese sulfate solution, then doping titanium-magnesium impurity and introducing complexing agent; the mixed mixture, ammonia solution and alkali liquor are added into a reaction kettle which is communicated with nitrogen in parallel for coprecipitation reaction, and mixed solution of the ammonia solution and the alkali liquor, 40-55% of the total volume of the reaction kettle, is filled in the reaction kettle in advance as bottom liquor; controlling the temperature in the reaction kettle at 50-55 ℃, controlling the pH value at 11 +/-0.5, and stopping the reaction when the granularity D50 of crystals generated by the coprecipitation reaction is 10 +/-1 um; and washing, drying, screening and deironing the obtained semi-finished slurry to obtain the Ti and Mg co-doped high-nickel ternary precursor. According to the invention, metal doping elements are directly introduced into the nickel-cobalt-manganese mixed solution, and a complexing agent is added, so that the metal elements are uniformly distributed in the high-granularity high-nickel ternary precursor, and the high-sphericity high-tap-density NCM811 type precursor containing Ti and Mg co-doped is prepared.

Description

Preparation method of Ti-Mg-containing co-doped NCM811 type precursor
Technical Field
The invention belongs to a lithium ion battery anode material, and particularly relates to a preparation method of a Ti and Mg co-doped high-nickel ternary precursor.
Background
Lithium ion secondary batteries have been widely used in electronic devices such as cameras, mobile phones, and notebook computers. In recent years, in order to power electric vehicles, more stringent requirements have been placed on such batteries, including higher specific capacity, longer cycle life, better rate capability and safety performance. The lithium ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode material of the lithium ion battery is generally considered as a main reason for limiting the capacity of the lithium battery and further limiting the driving mileage of the electric vehicle.
At present, the commercial battery anode materials in China mainly comprise lithium cobaltate, lithium manganate, lithium iron phosphate and conventional lithium nickel cobalt manganese oxide ternary materials, but the lithium nickel manganese oxide ternary materials cannot meet the higher energy requirement of the lithium ion battery, and the high nickel ternary anode materials (x) are high in nickel content>0.8) Li (Ni)xCoyMn1-x-y)O2Has higher specific capacity to meet the high energy requirement of the lithium ion battery. However, during the charge and discharge process of the high-nickel ternary material, Ni is generated2+Radius of ion
Figure BDA0003079927320000011
With Li + ions
Figure BDA0003079927320000012
Close, partially low-priced Ni2+Migration to Li+The position of (2) causes cation mixing and discharging, and hinders the de-intercalation process of lithium ions, thereby influencing the stability and conductivity of the ternary precursor. On the other hand, the high-nickel ternary precursor prepared by the existing preparation method generally has the problems of insufficient sphericity, low tap density, poor uniformity and the like.
Disclosure of Invention
In order to solve the problems, the invention provides a Ti and Mg co-doped high-nickel ternary precursor material and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a Ti and Mg-containing co-doped NCM811 type precursor comprises the following steps:
1) mixing nickel salt, cobalt salt, manganese salt, titanium salt and magnesium salt with a complexing agent to prepare a nickel-cobalt-manganese ternary solution containing titanium-magnesium codope;
2) introducing the mixed solution prepared in the step 1), alkali liquor and ammonia liquor into a reaction kettle which contains base liquor and is introduced with nitrogen or inert gas for coprecipitation reaction, wherein the pH value is controlled to be 10.5-11.5 in the reaction process;
3) stopping the reaction after crystal particles generated by the coprecipitation reaction grow to D50:10 +/-1 um, and filtering, washing and drying the prepared slurry to obtain the high-nickel ternary precursor containing Ti and Mg codoped with high sphericity and high tap density.
Preferably, the total concentration of the metal ions of nickel, cobalt and manganese in the step 1) is 1.8-2 mol/L, and the molar ratio of the metal ions of nickel, cobalt and manganese is 8:1: 1.
Preferably, the nickel salt, the cobalt salt and the manganese salt are respectively NiSO4、CoSO4、MnSO4。
Preferably, the doping amount of the magnesium salt in the step 1) is 0.01-0.5% of the total mass of the nickel, cobalt and manganese elements, and the doping amount of the titanium salt is 0.01-0.5% of the total mass of the nickel, cobalt and manganese elements.
Preferably, the magnesium salt is any one or combination of magnesium sulfate, magnesium chloride and magnesium nitrate, and the titanium salt is any one or combination of titanyl sulfate, titanium trichloride, titanium tetrachloride, titanium tetraiodide, titanium tetrabromide and titanium potassium oxalate.
Preferably, the complexing agent is any one or combination of a plurality of groups of succinic acid, malonic acid, malic acid, succinic acid, lactic acid, alkyl ethylidene diphosphonic acid and amino trimethylene phosphonic acid; the addition amount of the complexing agent is 1-5% of the total mass of the nickel, the cobalt and the manganese.
Preferably, the base solution in the step 2) is a mixture of sodium hydroxide and an aqueous ammonia solution, the molar concentration of the sodium hydroxide solution is 4.9-5.1mol/L, the concentration of the aqueous ammonia solution is 4.9-5.1mol/L, and the sodium hydroxide solution and the aqueous ammonia solution are mixed according to the volume ratio of 2: 1.
Preferably, the alkali solution in the step 2) is 5mol/L sodium hydroxide solution, the ammonia solution is 5mol/L ammonia water solution, and the flow ratio of the mixed solution, the ammonia water solution and the sodium hydroxide solution is 1:0.9-1.1: 0.9-1.1.
Preferably, the volume of the reaction kettle is 50L, and the bottom liquid accounts for 40-55% of the total volume of the reaction kettle; the flow rate of the mixed solution in the step 2) was 1.2L/h.
Preferably, the reaction temperature in step 2) is 50-55 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1) proper Mg doping in the process of preparing high-nickel precursor2+The mixed displacement degree of cations can be reduced, the crystal structure is effectively supported, and the structural stability is improved; ti4+The ion doping of (2) enlarges the lithium ion transmission channel, and Ti4+The valence state is higher, and the content of free electrons is increased after the nickel-cobalt-manganese ternary material is doped, so that the conductivity of the material is improved.
2) According to the invention, a proper amount of complexing agent is added, a certain amount of substrate is added into a reaction kettle, and meanwhile, a mixed solution, an ammonia water solution and a sodium hydroxide solution are added according to a certain flow ratio, so that doped Ti and Mg metal elements and nickel-cobalt-manganese elements form uniform coprecipitation, and uniform mixing at an atomic level is realized; the high nickel (Nimol% >0.8) ternary precursor with the advantages of high sphericity, high crystallinity, high tap and the like is prepared by reasonably setting process conditions.
Drawings
FIG. 1 is an electron micrograph of the NCM811 high-nickel precursor obtained in example 1, magnified 5000 times;
FIG. 2 is an electron micrograph of the NCM811 high-nickel precursor obtained in example 1 magnified 50000 times;
FIG. 3 is an XRD pattern of the NCM811 high nickel precursor made in example 1;
FIG. 4 is a graph comparing the cycle performance curves of the NCM811 high nickel precursor prepared in example 1 with the NCM811 high nickel precursor prepared without doping Ti and Mg.
The preparation method of the NCM811 high-nickel precursor prepared by undoped Ti and Mg is basically the same as that of the embodiment 1, except that magnesium sulfate and magnesium sulfate are not added.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Example 1
1) Mixing NiSO4、CoSO4、MnSO4Preparing a ternary solution, NiSO, with a total metal ion concentration of 2mol/L4、CoSO4、MnSO4The raw material molar ratio of (1) to (8);
2) adding 1% succinic acid complexing agent into the solution prepared in the step 1), and uniformly stirring for 10 min;
3) adding magnesium sulfate into the solution prepared in the step 2), wherein the doping amount is 0.3% of the total mass of the nickel, cobalt and manganese elements; simultaneously adding titanium sulfate with the doping amount of 0.3 percent of the total elements of nickel, cobalt and manganese, and uniformly stirring for 20 min;
4) adding 25L of 4.9-5.1mol/L ammonia water solution and 4.9-5.1mol/L sodium hydroxide solution in a volume ratio of 1:2 into a reaction kettle with a volume of 50L as a substrate.
5) Adding the mixed solution in the step 3), 5mol/L sodium hydroxide solution and 5mol/L ammonia water solution into a reaction kettle through a metering pump according to the flow ratio of 1:0.9:1.1, and maintaining the pH value in the reaction kettle at 11.2-11.3.
6) The rotation rate of the paddle in the reaction kettle is 800rpm, the reaction temperature is 55 ℃, and the reaction time is 50 h.
7) Stopping the machine after the granularity D50 of the overflowing product reaches 10 +/-1 um, completely discharging and filtering slurry in the reaction kettle, repeatedly cleaning the slurry with deionized water, and finally drying the slurry for 48 hours at 105 ℃ to obtain the NCM811 high-nickel precursor, wherein the specific physical and chemical performance parameters are shown in Table 1.
Example 2
1) Mixing NiSO4、CoSO4、MnSO4Preparing a ternary solution, NiSO, with a total metal ion concentration of 2mol/L4、CoSO4、MnSO4The raw material molar ratio of (1) to (8);
2) adding 1% succinic acid complexing agent into the solution prepared in the step 1), and uniformly stirring for 10 min;
3) adding magnesium sulfate into the solution prepared in the step 2), wherein the doping amount is 0.2% of the total mass of the nickel, cobalt and manganese elements; simultaneously adding titanium sulfate with the doping amount of 0.2 percent of the total elements of nickel, cobalt and manganese, and uniformly stirring for 20 min;
4) adding 20L of 4.9-5.1mol/L ammonia water solution and 4.9-5.1mol/L sodium hydroxide solution in a volume ratio of 1:2 into a reaction kettle with a volume of 50L as a substrate.
5) Adding the mixed solution in the step 3), 5mol/L sodium hydroxide solution and 5mol/L ammonia water solution into a reaction kettle through a metering pump according to the flow ratio of 1:1.1:0.9, and maintaining the pH value in the reaction kettle at 11.2-11.3.
6) The rotation rate of the paddle in the reaction kettle is 800rpm, the reaction temperature is 55 ℃, and the reaction time is 50 h.
7) Stopping the machine after the granularity D50 of the overflowing product reaches 10 +/-1 um, completely discharging and filtering slurry in the reaction kettle, repeatedly cleaning the slurry with deionized water, and finally drying the slurry for 48 hours at 105 ℃ to obtain the NCM811 high-nickel precursor, wherein the specific physical and chemical performance parameters are shown in Table 1.
Example 3
1) Mixing NiSO4、CoSO4、MnSO4Preparing a ternary solution, NiSO, with a total metal ion concentration of 2mol/L4、CoSO4、MnSO4The raw material molar ratio of (1) to (8);
2) adding 2% malic acid complexing agent into the solution prepared in the step 1), and uniformly stirring for 10 min;
3) adding magnesium sulfate into the solution prepared in the step 2), wherein the doping amount is 0.3% of the total mass of the nickel, cobalt and manganese elements; simultaneously adding titanium sulfate with the doping amount of 0.3 percent of the total elements of nickel, cobalt and manganese, and uniformly stirring for 20 min;
4) adding 25L of 4.9-5.1mol/L ammonia water solution and 4.9-5.1mol/L sodium hydroxide solution in a volume ratio of 1:2 into a reaction kettle with a volume of 50L as a substrate.
5) Adding the mixed solution in the step 3), 5mol/L sodium hydroxide solution and 5mol/L ammonia water solution into a reaction kettle through a metering pump according to the flow ratio of 1:1.1:1, and maintaining the pH value in the reaction kettle at 11-11.2.
6) The rotation rate of the paddle in the reaction kettle is 800rpm, the reaction temperature is 55 ℃, and the reaction time is 50 h.
7) Stopping the machine after the granularity D50 of the overflowing product reaches 10 +/-1 um, completely discharging and filtering slurry in the reaction kettle, repeatedly cleaning the slurry with deionized water, and finally drying the slurry for 48 hours at 105 ℃ to obtain the NCM811 high-nickel precursor, wherein the specific physical and chemical performance parameters are shown in Table 1.
Example 4
1) Mixing NiSO4、CoSO4、MnSO4Preparing a ternary solution, NiSO, with a total metal ion concentration of 2mol/L4、CoSO4、MnSO4The raw material molar ratio of (1) to (8);
2) adding 2% malic acid complexing agent into the solution prepared in the step 1), and uniformly stirring for 10 min;
3) adding magnesium sulfate into the solution prepared in the step 2), wherein the doping amount is 0.1 percent of the total mass of the nickel, cobalt and manganese elements; simultaneously adding titanium sulfate with the doping amount of 0.1 percent of the total elements of nickel, cobalt and manganese, and uniformly stirring for 20 min;
4) adding 20L of 4.9-5.1mol/L ammonia water solution and 4.9-5.1mol/L sodium hydroxide solution in a volume ratio of 1:2 into a reaction kettle with a volume of 50L as a substrate.
5) Adding the mixed solution obtained in the step 3), 5mol/L sodium hydroxide solution and 5mol/L ammonia water solution into a reaction kettle through a metering pump according to the flow ratio of 1:0.9:1, and maintaining the pH value in the reaction kettle at 11.0-11.2.
6) The rotation rate of the paddle in the reaction kettle is 800rpm, the reaction temperature is 55 ℃, and the reaction time is 50 h.
7) Stopping the machine after the granularity D50 of the overflowing product reaches 10 +/-1 um, completely discharging and filtering slurry in the reaction kettle, repeatedly cleaning the slurry with deionized water, and finally drying the slurry for 48 hours at 105 ℃ to obtain the NCM811 high-nickel precursor, wherein the specific physical and chemical performance parameters are shown in Table 1.
Example 5
1) Mixing NiSO4、CoSO4、MnSO4Preparing a ternary solution, NiSO, with a total metal ion concentration of 2mol/L4、CoSO4、MnSO4The raw material molar ratio of (1) to (8);
2) adding 1% of lactic acid complexing agent into the solution prepared in the step 1), and uniformly stirring for 10 min;
3) adding magnesium sulfate into the solution prepared in the step 2), wherein the doping amount is 0.1 percent of the total mass of the nickel, cobalt and manganese elements; simultaneously adding titanium sulfate with the doping amount of 0.1 percent of the total elements of nickel, cobalt and manganese, and uniformly stirring for 20 min;
4) adding 20L of 4.9-5.1mol/L ammonia water solution and 4.9-5.1mol/L sodium hydroxide solution in a volume ratio of 1:2 into a reaction kettle with a volume of 50L as a substrate.
5) Adding the mixed solution in the step 3), 5mol/L sodium hydroxide solution and 5mol/L ammonia water solution into a reaction kettle through a metering pump according to the flow ratio of 1:1.1:1.1, and maintaining the pH value in the reaction kettle at 11.0-11.2.
6) The rotation rate of the paddle in the reaction kettle is 800rpm, the reaction temperature is 55 ℃, and the reaction time is 50 h.
7) Stopping the machine after the granularity D50 of the overflowing product reaches 10 +/-1 um, completely discharging and filtering slurry in the reaction kettle, repeatedly cleaning the slurry with deionized water, and finally drying the slurry for 48 hours at 105 ℃ to obtain the NCM811 high-nickel precursor, wherein the specific physical and chemical performance parameters are shown in Table 1.
Example 6
1) Mixing NiSO4、CoSO4、MnSO4Preparing a ternary solution, NiSO, with a total metal ion concentration of 2mol/L4、CoSO4、MnSO4The raw material molar ratio of (1) to (8);
2) adding 2% of lactic acid complexing agent into the solution prepared in the step 1), and uniformly stirring for 10 min;
3) adding magnesium sulfate into the solution prepared in the step 2), wherein the doping amount is 0.2% of the total mass of the nickel, cobalt and manganese elements; simultaneously adding titanium sulfate with the doping amount of 0.2 percent of the total elements of nickel, cobalt and manganese, and uniformly stirring for 20 min;
4) adding 25L of 4.9-5.1mol/L ammonia water solution and 4.9-5.1mol/L sodium hydroxide solution in a volume ratio of 1:2 into a reaction kettle with a volume of 50L as a substrate.
5) Adding the mixed solution obtained in the step 3), 5mol/L sodium hydroxide solution and 5mol/L ammonia water solution into a reaction kettle through a metering pump according to the flow ratio of 1:0.9:0.9, and maintaining the pH value in the reaction kettle at 11.0-11.2.
6) The rotation rate of the paddle in the reaction kettle is 800rpm, the reaction temperature is 55 ℃, and the reaction lasts 50 h.
7) Stopping the machine after the granularity D50 of the overflowing product reaches 10 +/-1 um, completely discharging and filtering slurry in the reaction kettle, repeatedly cleaning the slurry with deionized water, and finally drying the slurry for 48 hours at 105 ℃ to obtain the NCM811 high-nickel precursor, wherein the specific physical and chemical performance parameters are shown in Table 1.
Table-physicochemical property parameter table
Figure BDA0003079927320000081
As can be seen from fig. 3, the NCM811 high nickel precursor prepared by doping Ti and Mg has better battery cycle performance than the high nickel precursor prepared by doping non-Ti and Mg.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not substantially depart from the spirit and scope of the present invention as defined by the appended claims.

Claims (10)

1. A preparation method of a Ti and Mg-containing co-doped NCM811 type precursor is characterized by comprising the following steps:
1) mixing nickel salt, cobalt salt, manganese salt, titanium salt and magnesium salt with a complexing agent to prepare a nickel-cobalt-manganese ternary solution containing titanium-magnesium codope;
2) introducing the mixed solution prepared in the step 1), alkali liquor and ammonia liquor into a reaction kettle containing base liquor and introduced with nitrogen or inert gas for coprecipitation reaction, wherein the pH value is controlled to be 11 +/-0.5 in the reaction process;
3) stopping the reaction after crystal particles generated by the coprecipitation reaction grow to D50:10 +/-1 um, and filtering, washing and drying the prepared slurry to obtain the high-nickel ternary precursor containing Ti and Mg codoped with high sphericity and high tap density.
2. The preparation method of the Ti-and Mg-containing co-doped NCM811 type precursor as claimed in claim 1, wherein the total concentration of the metal ions of nickel, cobalt and manganese in step 1) is 1.8mol-2mol/L, and the molar ratio of the metal ions of nickel, cobalt and manganese is 8:1: 1.
3. The method for preparing the Ti-and Mg-codoped NCM811 type precursor according to claim 2, wherein the nickel salt, the cobalt salt and the manganese salt are respectively NiSO4、CoSO4、MnSO4。
4. The preparation method of the Ti-and Mg-codoped NCM811 type precursor as claimed in claim 2, wherein the magnesium salt is added in an amount of 0.01-0.5% of the total mass of the nickel, cobalt and manganese elements in step 1), and the titanium salt is added in an amount of 0.01-0.5% of the total mass of the nickel, cobalt and manganese elements.
5. The preparation method of the Ti-Mg co-doped NCM811 type precursor as claimed in claim 4, wherein the magnesium salt is any one or more of magnesium sulfate, magnesium chloride and magnesium nitrate, and the titanium salt is any one or more of titanyl sulfate, titanium trichloride, titanium tetrachloride, titanium tetraiodide, titanium tetrabromide and titanium potassium oxalate.
6. The preparation method of the precursor containing Ti and Mg co-doped NCM811, according to claim 1, wherein the complexing agent is any one or more of succinic acid, malonic acid, malic acid, succinic acid, lactic acid, alkyl ethylidene diphosphonic acid, and amino trimethylene phosphonic acid; the addition amount of the complexing agent is 1-5% of the total mass of the nickel, the cobalt and the manganese.
7. The preparation method of the Ti-and Mg-codoped NCM811 type precursor as claimed in claim 2, wherein the base solution in the step 2) is a mixture of sodium hydroxide and an aqueous ammonia solution, the molar concentration of the sodium hydroxide solution is 4.9-5.1mol/L, the concentration of the aqueous ammonia solution is 4.9-5.1mol/L, and the sodium hydroxide solution and the aqueous ammonia solution are mixed in a volume ratio of 2: 1.
8. The preparation method of the Ti-and Mg-containing co-doped NCM811 type precursor according to claim 7, wherein the alkali solution in the step 2) is a 5mol/L sodium hydroxide solution, the ammonia solution is a 5mol/L ammonia water solution, and the flow ratio of the mixed solution, the ammonia water solution and the sodium hydroxide solution is 1:0.9-1.1: 0.9-1.1.
9. The preparation method of the Ti and Mg co-doped NCM811 type precursor as claimed in claim 8, wherein the volume of the reaction kettle is 50L, and the base solution accounts for 40-55% of the total volume of the reaction kettle; the flow rate of the mixed solution in the step 2) is 1.2L/h.
10. The preparation method of the precursor containing Ti and Mg co-doped NCM811 type according to claim 1, wherein the reaction temperature in step 2) is 50-55 ℃.
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