CN115057489A - Cobalt-free positive electrode material, precursor thereof and preparation method - Google Patents
Cobalt-free positive electrode material, precursor thereof and preparation method Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- 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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Abstract
The invention belongs to the technical field of battery materials, and discloses a cobalt-free anode material, a precursor thereof and a preparation method thereof. The precursor of the cobalt-free anode material comprises an inner core and an outer shell, wherein the inner core is Ni (OH) 2 The outer shell is made of Mg (OH) 2 And Al (OH) 3 And (4) the components are combined together. Regulating Ni (OH) by surfactant in the preparation process of precursor 2 Surface state of (1) Mg 2+ And AlO 2 ‑ In-situ double hydrolysis reaction occurs on the surface. And sintering the precursor with a lithium source to obtain the NiMgAl anode material. The anode material can not only realize cobalt-freeThe cost of the battery is reduced, the high voltage performance can be realized, the specific energy of the battery system is improved, and the high specific energy of the battery is realized.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a high-voltage cobalt-free precursor, a high-voltage cobalt-free anode material and a preparation method of the high-voltage cobalt-free precursor.
Background
The overuse of non-renewable fossil fuels and the resulting environmental problems have led to the recognition of the importance of renewable clean energy sources. Lithium ion batteries are a clean energy storage system, and are especially important in the modern times of clean energy. In the whole lithium ion battery, the positive electrode material occupies a half-wall Jiangshan, and the performance of the positive electrode material directly determines the performance of the whole battery. High nickel ternary positive electrode materials (such as NiCoMn and NiCoAl series) which have been developed gradually in recent years are receiving much attention due to their high specific energy. Most of the ternary cathode materials in the current mainstream contain Co, however, Co is extremely expensive, and the cost of the battery is greatly increased. In addition, the high nickel ternary material is easy to generate irreversible phase change and serious interface side reaction under high charging voltage, and has poor high voltage performance. Therefore, it is very important to develop a cobalt-free positive electrode material with excellent high voltage performance.
Disclosure of Invention
In view of the problems of the prior art, a first object of the present invention is to provide a precursor of a cobalt-free cathode material.
The second purpose of the invention is to provide a preparation method of the precursor of the cobalt-free cathode material.
The third purpose of the invention is to provide a high-voltage cobalt-free cathode material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following specific technical solutions.
Firstly, the invention provides a precursor of a cobalt-free anode material, which comprises an inner core and an outer shell, wherein the inner core is Ni (OH) 2 The outer shell is made of Mg (OH) 2 And Al (OH) 3 The components are combined together; the chemical general formula of the precursor is Ni 1-x-y Mg x Al y (OH) 2 Wherein, 0<x<0.2，0<y<0.4。
The invention further provides a preparation method of the precursor of the cobalt-free cathode material, which comprises the following steps:
step S1, mixing Ni (OH) 2 Adding the anionic surfactant and the deionized water into the mixture, and stirring the mixture to form a suspension;
step S2, adding magnesium salt into the suspension obtained in the step S1, and stirring to obtain a feed liquid;
step S3, slowly adding an aluminate solution into the feed liquid obtained in the step S2, and aging for a period of time to obtain precursor slurry;
and step S4, filtering the precursor slurry, and washing and drying the solid phase to obtain the precursor.
Based on the same inventive concept, the invention also provides another preparation method of the precursor of the cobalt-free cathode material, which comprises the following steps:
step S1, mixing Ni (OH) 2 Adding the cationic surfactant and the deionized water into the mixture, and stirring the mixture to form a suspension;
step S2, adding an aluminate solution into the suspension obtained in the step S1, and stirring to obtain a feed liquid;
step S3, slowly adding a magnesium salt solution into the feed liquid obtained in the step S2, and aging for a period of time to obtain precursor slurry;
and step S4, filtering the precursor slurry, and washing and drying the solid phase to obtain the precursor.
Further, in some preferred embodiments of the present invention, in step S1, Ni (OH) 2 And the addition molar ratio of the anionic surfactant to the anionic surfactant is 100 (1-10).
Preferably, the anionic surfactant is one or more of polyvinylpyrrolidone (PVP), polyacrylamide, fatty acid salt and sulfonate.
Further, in some preferred embodiments of the present invention, in step S1, Ni (OH) 2 And the addition molar ratio of the cationic surfactant to the cationic surfactant is 100 (1-10).
Preferably, the cationic surfactant is one or more of amine salt type, quaternary ammonium salt type, heterocyclic type and xanthate type cationic surfactant.
Further, in some preferred embodiments of the present invention, the magnesium salt is one or more of magnesium chloride, magnesium nitrate, magnesium acetate, and magnesium citrate.
Further, in some preferred embodiments of the present invention, the aluminate is one or both of potassium aluminate and sodium aluminate.
Further, in some preferred embodiments of the present invention, the concentration of the aluminate solution is 0.2 to 1mol/L, and the addition rate of the aluminate solution is 0.05 to 5 ml/min.
Further, in some preferred embodiments of the invention, the amounts of aluminate and magnesium salt follow the following relationship: AlO (aluminum oxide) 2 - And Mg 2+ The molar ratio of (2-3): 1.
further, in some preferred embodiments of the present invention, in step S3, the aging time is 1 to 6 hours.
To achieve the third object of the present invention, the present invention provides the following technical solutions.
A cobalt-free anode material with a chemical general formula of Li 1-x Mg x Ni 1-y Al y O 2 Wherein 0 is<x<0.2，0<y<0.4, Mg and Li occupy the same site, and Ni and Al are in the same site.
Further, the cobalt-free cathode material is prepared by the following method: and uniformly mixing the precursor of the prepared cobalt-free cathode material with lithium salt, and sintering to obtain the cobalt-free cathode material.
Further, in some preferred embodiments of the present invention, the lithium salt is one or two or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, or lithium citrate.
Further, in some preferred embodiments of the present invention, the precursor and lithium salt are dosed according to the following relationship: the ratio of the sum of the amounts of Ni and Al elements to the amount of Li element is 1 (1-1.08).
Further, in some preferred embodiments of the present invention, the sintering manner is: firstly, presintering for 2-8 hours at the temperature of 300-600 ℃, and then sintering for 6-15 hours at the temperature of 650-750 ℃.
Further, in some preferred embodiments of the present invention, the sintering atmosphere is an atmosphere having an oxygen content of 21% to 100%.
The invention regulates Ni (OH) through a surfactant 2 Surface state of (1) Mg 2+ And AlO 2 - In-situ double hydrolysis reaction occurs on the surface to obtain uniform coating Mg (OH) 2 And Al (OH) 3 Ni (OH) 2 And (5) compounding the precursor. And then sintering the NiMgAl ternary cathode material with a lithium source to obtain the NiMgAl ternary cathode material. Al is doped at the Ni site, so that cation mixing can be inhibited, and the structural stability of the material is improved. Mg is doped at Li sites, so that the phase change of the anode material under high voltage is inhibited, and excellent high voltage performance is further shown.
Compared with the prior art, the technical scheme provided by the invention has the following obvious beneficial effects:
（1）Mg 2+ and AlO 2 - In the presence of Ni (OH) 2 The surface is subjected to in-situ double hydrolysis reaction, and the pH value or potential of a reaction system is not required to be adjusted by ammonia water, alkali solution and the like;
(2) the NiMgAl positive electrode material not only can realize cobalt-free of the positive electrode material and reduce the cost of the battery, but also can realize high voltage performance, improve the specific energy of a battery system and realize high specific energy of the battery;
(3) the process flow for preparing the precursor and the anode material is simple, short and strong in universality, and is suitable for large-scale industrial production.
Drawings
Fig. 1 is a schematic diagram of the process for preparing the precursor and the anode material according to the present invention.
FIG. 2 is an SEM photograph of the precursor obtained in example 1, wherein the magnification of the a-picture is 2000, the magnification of the b-picture is 10000, and the magnification of the c-picture is 20000.
Fig. 3 is an SEM image of the positive electrode material obtained in example 1, in which the magnification of the a-picture is 2000, the magnification of the b-picture is 10000, and the magnification of the c-picture is 20000.
FIG. 4 shows a positive electrode material obtained in example 1 and a commercially available LiNiO 2 The cycle performance curve of the battery of (1).
FIG. 5 shows a positive electrode material obtained in example 5 and a commercially available LiNiO 2 The cycle performance curve of the battery of (1).
Detailed Description
In order to facilitate an understanding of the invention, reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings, and the scope of the invention is not limited to the following specific embodiments.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
As shown in FIG. 1, in the preparation of a cobalt-free positive electrode material precursor, Ni (OH) is treated with a surfactant 2 Regulation of Ni (OH) 2 Surface state of (2), then adding magnesium salt, Mg 2+ Under the action of surfactant, Ni (OH) is greatly existed 2 Of (2) is provided. Then aluminate is added to realize Mg 2+ And AlO 2 - In the presence of Ni (OH) 2 The surface generates in-situ double hydrolysis reaction without adjusting the pH value or potential of the reaction system by ammonia water, alkali solution and the like. And mixing and sintering the precursor and lithium salt to obtain the cathode material.
Example 1
The embodiment comprises the following steps:
step S1, take 20g of spherical Ni (OH) 2 And 0.8g of PVP anionic surfactant, adding into 100ml of deionized water, and stirring for 1 hour to form suspension;
step S2, adding 0.3319g of anhydrous magnesium chloride into the suspension in the step S1, and continuously stirring for 1 hour to obtain feed liquid;
step S3, adding 0.1 mL/min to the feed liquid in step S2 -1 At a flow rate of 40mL of 0.5mol L -1 Then aging the sodium aluminate solution for 2 hours to obtain precursor slurry;
step S4, carrying out suction filtration on the precursor slurry, washing the solid phase for multiple times by using deionized water, and then drying the solid phase for 12 hours at the temperature of 120 ℃ to obtain a precursor;
step S5, according to the proportion that the sum of the amounts of Ni and Al element substances and the amount of Li element substances are 1:1.05, the dried precursor and a lithium source LiOH & H 2 And O is uniformly mixed, presintering is carried out for 5 hours at 480 ℃ in the environment of high purity oxygen, and sintering is carried out for 12 hours at 720 ℃ to obtain the high-voltage cobalt-free cathode material.
FIG. 2 is an SEM image of the precursor obtained in step S4, in which spherical Ni (OH) is observed 2 Surface containing Mg (OH) uniformly coated 2 And Al (OH) 3 。
FIG. 3 is an SEM image of the cathode material obtained in step S5, and it can be seen that the NiMgAl ternary cathode material consists of secondary spheres of 3-20 μm, and the surface of the spheres consists of primary spheres of approximately 200 nm.
The positive electrode material obtained in example 1 and commercially available LiNiO were used 2 The button cells were assembled by the same method as is conventional in the art and tested for electrochemical performance. Fig. 4 is a graph of the resulting cycle performance. As can be seen from FIG. 4, the specific discharge capacity of the battery comprising the positive electrode material obtained in example 1 was maintained at 122.2 mAh/g or more, and the battery comprising commercially available LiNiO was maintained at a specific discharge capacity of 122.2 mAh/g, when the battery was cycled for 500 cycles at a cut-off voltage of 2.8 to 4.6V under 1C-rate charge and discharge 2 The capacity of the battery is only 67.4 mAh/g after 100 cycles of circulation. The cathode material prepared in example 1 has excellent high voltage cycling stability, and can be used as a high voltage cathode material.
Example 2
The embodiment comprises the following steps:
step S1, take 10g of spherical Ni (OH) 2 Adding 0.5g of polyacrylamide anionic surfactant into 50ml of deionized water, and stirring for 1 hour to form suspension;
step S2, adding 0.2346g of anhydrous magnesium nitrate into the suspension in the step S1, and continuously stirring for 1 hour to obtain feed liquid;
step S3, adding 0.2 mL/min to the feed liquid in step S2 -1 At a flow rate of 25mL of a 0.4mol L concentration -1 Of potassium aluminateContinuing aging for 2h to obtain precursor slurry;
step S4, carrying out suction filtration on the precursor slurry, washing the solid phase for multiple times by using deionized water, and then drying the solid phase for 12 hours at the temperature of 120 ℃ to obtain a precursor;
step S5, according to the proportion that the sum of the amounts of Ni and Al element substances and the amount of Li element substances are 1:1.03, the dried precursor and a lithium source LiOH & H 2 And O is uniformly mixed, presintering is carried out for 4 hours at the temperature of 500 ℃ in the environment of high purity oxygen, and sintering is carried out for 10 hours at the temperature of 750 ℃ to obtain the high-voltage cobalt-free cathode material.
Example 3
The embodiment comprises the following steps:
step S1, take 50g of spherical Ni (OH) 2 And 3g of polyvinylpyrrolidone anionic surfactant, and adding the polyvinylpyrrolidone anionic surfactant into 250ml of deionized water, and stirring for 1 hour to form a suspension;
step S2, adding 0.2342g of anhydrous magnesium acetate into the suspension in the step S1, and continuously stirring for 1 hour to obtain feed liquid;
step S3, adding 1 mL/min of the solution in step S2 -1 At a flow rate of 200mL of 1mol L -1 Then, continuously aging the sodium aluminate solution for 2 hours to obtain precursor slurry;
step S4, carrying out suction filtration on the precursor slurry, washing the solid phase for multiple times by using deionized water, and then drying the solid phase for 12 hours at the temperature of 120 ℃ to obtain a precursor;
step S5, according to the proportion that the sum of the amounts of Ni and Al element substances and the amount of Li element substances are 1:1.08, the dried precursor and a lithium source LiOH & H 2 And O is uniformly mixed, presintering is carried out for 6 hours at the temperature of 450 ℃ in the environment of high purity oxygen, and sintering is carried out for 15 hours at the temperature of 700 ℃ to obtain the high-voltage cobalt-free cathode material.
Example 4
The embodiment comprises the following steps:
step S1, take 10g of spherical Ni (OH) 2 And 0.5g of PVP anionic surfactant, adding into 100ml of deionized water, and stirring for 1 hour to form suspension;
step S2, adding 0.3319g of anhydrous magnesium chloride into the suspension in the step S1, and continuously stirring for 1 hour to obtain feed liquid;
step S3, adding 0.1 mL/min to the feed liquid in step S2 -1 At a flow rate of 40mL of 0.5mol L -1 Then aging the sodium aluminate solution for 2 hours to obtain precursor slurry;
step S4, carrying out suction filtration on the precursor slurry, washing the solid phase for multiple times by using deionized water, and then drying the solid phase for 12 hours at the temperature of 120 ℃ to obtain a precursor;
step S5, according to the proportion that the sum of the amounts of Ni and Al element substances and the amount of Li element substances are 1:1.05, the dried precursor and a lithium source LiOH & H 2 And O is uniformly mixed, presintering is carried out for 5 hours at 480 ℃ in the environment of high purity oxygen, and sintering is carried out for 12 hours at 720 ℃ to obtain the high-voltage cobalt-free cathode material.
Example 5
The present embodiment comprises the following steps:
step S1, take 15g of spherical Ni (OH) 2 And 4.2g of octadecyl dimethyl benzyl ammonium chloride cationic surfactant (quaternary ammonium salt type), adding into 150ml of deionized water, and stirring for 1h to form a suspension;
step S2, adding 0.5123g of sodium aluminate into the suspension in the step S1, and continuing stirring for 1 hour to obtain feed liquid;
step S3, adding 0.2 mL/min to the feed liquid in step S2 -1 At a flow rate of 60mL of 0.3mol L -1 Then, continuously aging the magnesium chloride solution for 2 hours to obtain precursor slurry;
step S4, carrying out suction filtration on the precursor slurry, washing the solid phase for multiple times by using deionized water, and then drying the solid phase for 12 hours at the temperature of 120 ℃ to obtain a precursor;
step S5, according to the proportion that the sum of the amounts of Ni and Al element substances and the amount of Li element substances are 1:1.04, the dried precursor and a lithium source LiOH & H 2 And O is uniformly mixed, presintering is carried out for 4 hours at the temperature of 500 ℃ in the environment of high purity oxygen, and sintering is carried out for 12 hours at the temperature of 700 ℃ to obtain the high-voltage cobalt-free cathode material.
The positive electrode material obtained in example 5 and commercially available LiNiO were used 2 Through the field ofThe button cell was assembled in the same manner as in the conventional manner and tested for electrochemical performance. Fig. 5 is a graph of the obtained rate capability. As can be seen from FIG. 5, the rate capability of the battery containing the positive electrode material obtained in example 5 is significantly better than that of the battery containing commercially available LiNiO at a cut-off voltage of 2.8 to 4.6V 2 The rate capability of the battery of (1). The specific capacity is 148.9 mAh/g under the multiplying power of 10C and is much higher than LiNiO 2 101.9 mAh/g. The cathode material prepared in example 5 has excellent high-voltage electrochemical performance and can be used as a high-voltage cathode material.
While the foregoing is directed to the preferred embodiment of the present invention, it will be appreciated by those skilled in the art that various changes and modifications may be made therein without departing from the principles of the invention as set forth in the appended claims.
Claims (10)
1. The precursor of the cobalt-free cathode material is characterized by comprising an inner core and an outer shell, wherein the inner core is Ni (OH) 2 The outer shell is made of Mg (OH) 2 And Al (OH) 3 And (4) the components are combined together.
2. A preparation method of a precursor of a cobalt-free cathode material is characterized by comprising the following steps:
step S1, mixing Ni (OH) 2 Adding the anionic surfactant and the deionized water into the mixture, and stirring the mixture to form a suspension;
step S2, adding magnesium salt into the suspension obtained in the step S1, and stirring to obtain a feed liquid;
step S3, slowly adding an aluminate solution into the feed liquid obtained in the step S2, and aging for a period of time to obtain precursor slurry;
and step S4, filtering the precursor slurry, and washing and drying the solid phase to obtain the precursor.
3. A preparation method of a precursor of a cobalt-free cathode material is characterized by comprising the following steps:
step S1, adding Ni (OH)) 2 Adding the cationic surfactant and the deionized water into the mixture, and stirring the mixture to form a suspension;
step S2, adding an aluminate solution into the suspension obtained in the step S1, and stirring to obtain a feed liquid;
step S3, slowly adding a magnesium salt solution into the feed liquid obtained in the step S2, and aging for a period of time to obtain precursor slurry;
and step S4, filtering the precursor slurry, and washing and drying the solid phase to obtain the precursor.
4. The method according to claim 2, wherein in step S1, Ni (OH) 2 And the addition molar ratio of the anionic surfactant to the anionic surfactant is 100 (1-10); the anionic surfactant is one or more of polyvinylpyrrolidone (PVP), polyacrylamide, fatty acid salt and sulfonate.
5. The method according to claim 3, wherein in step S1, Ni (OH) 2 The adding molar ratio of the cationic surfactant to the cationic surfactant is 100 (1-10); the cationic surfactant is one or more of amine salt type, quaternary ammonium salt type, heterocyclic type and zero-salt type cationic surfactant.
6. The preparation method according to claim 2 or 3, wherein the magnesium salt is one or more of magnesium chloride, magnesium nitrate, magnesium acetate and magnesium citrate; the aluminate is one or two of potassium aluminate and sodium aluminate.
7. The method according to claim 6, wherein the concentration of the aluminate solution is 0.2 to 1mol/L, and the addition rate of the aluminate solution is 0.05 to 5 ml/min; the amounts of aluminate and magnesium salt used follow the following relationship: AlO (aluminum oxide) 2 - And Mg 2+ The molar ratio of (2-3): 1.
8. a cobalt-free positive electrode material, characterized in that the positive electrode materialThe chemical general formula of the electrode material is Li 1-x Mg x Ni 1-y Al y O 2 Wherein, 0<x<0.2，0<y<0.4; mg and Li occupy the same site, and Ni and Al are in the same site.
9. The positive electrode material according to claim 8, which is prepared by the following method: uniformly mixing a precursor of the cobalt-free cathode material according to claim 1 or a precursor of the cobalt-free cathode material prepared by the preparation method according to any one of claims 2 to 7 with a lithium salt, and then sintering to obtain the cobalt-free cathode material; the sintering mode is as follows: firstly, presintering for 2-8 hours at the temperature of 300-600 ℃, and then sintering for 6-15 hours at the temperature of 650-750 ℃; the sintering atmosphere is an atmosphere with the oxygen content of 21% -100%.
10. The positive electrode material according to claim 9, wherein the precursor and the lithium salt are formulated in accordance with the following relationship: the ratio of the sum of the amounts of Ni and Al elements to the amount of Li element is 1 (1-1.08).
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