CN111977707A - Lithium-intercalated nickel-containing metal oxide and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the field of lithium ion batteries, and relates to a lithium-intercalated nickel-containing metal oxide, and a preparation method and application thereof. The preparation method of the lithium intercalation nickel-containing metal oxide comprises the following steps: s1, pre-sintering a nickel source at 200-500 ℃ for 2-10 hours in an oxidizing atmosphere to obtain a nickel-containing precursor; s2, mixing the nickel-containing precursor with an alkali metal compound, an oxidant, water and optional additives, and then carrying out lithium intercalation reaction, wherein the alkali metal compound at least comprises a lithium compound, so that alkali metal ions are intercalated into the nickel-containing precursor to form solid solution metal salt, and after the lithium intercalation reaction is finished, carrying out solid-liquid separation, and calcining the obtained solid product. The lithium-intercalated nickel-containing metal oxide prepared by the method provided by the invention is used as the anode material of the lithium ion battery, so that the first discharge capacity and the capacity retention rate of the lithium ion battery can be effectively improved, and the method has great industrial application prospects.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a lithium-intercalated nickel-containing metal oxide, and a preparation method and application thereof.
Background
With the application of lithium ion batteries in electric automobiles, battery materials are more and more emphasized, the structure and the performance of the anode material become key factors for application in the field of electric automobiles, the development of the anode material with high capacity, high cycle performance, high safety and long service life is a main development direction in the future, and meanwhile, higher requirements are provided for the anode material of the battery. The multi-component cathode material has been gradually started to be applied to the 3C field, wherein matsushita, korea LG has succeeded in mass-applying the multi-component cathode material to electric vehicles.
With the rapid development of lithium ion batteries, the requirements on the cathode material are increasing, and especially higher requirements on the uniformity of the components and the phase structure of the cathode material are provided. The performance of the battery anode material directly influences the electrical performance of the battery, and in order to improve the performance of the anode material, the most researches are carried out in the prior art by optimizing a precursor, optimizing a sintering process and optimizing a doping and coating means, but the material uniformity cannot reach the most ideal state. The coprecipitation crystallization technique can improve the homogenization of phase components to some extent, but sintering of lithium metal elements during lithiation cannot achieve optimal homogenization. An important technical index in the lithiation process is the uniform distribution of lithium metal, because the uniform distribution of lithium directly affects the capacity, cycle, rate, safety and other properties of the battery anode material. At present, the problem of uniform distribution of lithium element is mainly solved by adjusting sintering temperature, atmosphere, time, charging amount and the like. In the positive electrode material system containing no nickel, lithium is easy to be inserted into crystal lattices to realize uniform distribution. However, for a positive electrode material system containing nickel, a high-temperature high-pressure lithium intercalation process is generally required, and even if the high-temperature high-pressure lithium intercalation process is adopted, it is difficult for lithium element to reach an ideal uniform distribution state, so that the first discharge capacity and the capacity retention rate of the lithium ion battery obtained by the method are low.
Disclosure of Invention
The invention aims to overcome the defects that the prior nickel-containing anode material system needs a high-temperature high-pressure process to embed lithium and lithium element is difficult to achieve an ideal uniform distribution state, so that the initial discharge capacity and the capacity retention rate of the obtained lithium ion battery are lower, and provides a nickel-containing metal oxide which can realize good lithium embedding only at normal temperature and normal pressure, and a preparation method and application thereof, so that the initial discharge capacity and the capacity retention rate of the lithium ion battery corresponding to the obtained lithium-embedded nickel-containing metal oxide are very high.
After intensive research, the inventor of the invention finds that, before lithium intercalation, nickel is firstly presintered at a specific temperature of 200-500 ℃, and then the obtained nickel-containing precursor, an alkali metal compound, an oxidant, water and an optional additive are subjected to lithium intercalation reaction, so that the first discharge capacity and the capacity retention rate of a lithium ion battery can be remarkably improved. The reason for this is presumed to be due to: for a positive electrode material system containing nickel, the root cause of the difficulty in uniform distribution of lithium element is that the lithium element is difficult to be inserted into the crystal lattice due to the special crystal form of lithium nickelate, a high-temperature and high-pressure lithium insertion process is usually required, and even if the high-temperature and high-pressure lithium insertion process is adopted, the lithium element is difficult to reach an ideal uniform distribution state, but lithium gradient difference is easily formed on active particles, namely the concentration of the lithium element in the active particles is gradually reduced from outside to inside, so that the first discharge capacity and the capacity retention rate of the lithium ion battery obtained by the method are low; for a nickel-containing anode material system, before lithium intercalation, nickel is pre-sintered at a specific temperature of 200-500 ℃, an obtained nickel-containing precursor can be converted into an amorphous state from an original crystalline state, the diffusion of lithium elements is facilitated in a subsequent lithium intercalation process, then the obtained nickel-containing precursor, an alkali metal compound, an oxidant, water and an optional additive are subjected to lithium intercalation reaction, countless micro-primary batteries are formed due to the redox potential difference of nickel and the oxidant, the concentration gradient of lithium can be weakened by the loose state of the nickel-containing precursor and a wet redox system, uniform distribution is realized, and the lithium is ensured to be successfully intercalated into a crystal lattice retention rate of a metal oxide to obtain crystalline lithium nickelate, so that the first discharge capacity and the capacity of the lithium ion battery are improved. Based on this, the present invention has been completed.
Specifically, the invention provides a preparation method of a lithium-intercalated nickel-containing metal oxide, which comprises the following steps:
s1, pre-sintering a nickel source at 200-500 ℃ for 2-10 hours in an oxidizing atmosphere to obtain a nickel-containing precursor;
s2, mixing the nickel-containing precursor with an alkali metal compound, an oxidant, water and optional additives, and then carrying out lithium intercalation reaction, wherein the alkali metal compound at least comprises a lithium compound, so that alkali metal ions are intercalated into the nickel-containing precursor to form solid solution metal salt, carrying out solid-liquid separation after the lithium intercalation reaction is finished, and calcining the obtained solid product to obtain the lithium-intercalated and nickel-containing metal oxide.
In the present invention, the metal element in the nickel source preferably includes at least one of cobalt, manganese and aluminum in addition to nickel, and for example, may be nickel cobalt, nickel manganese, nickel aluminum, nickel cobalt manganese, nickel cobalt aluminum, nickel manganese aluminum or a nickel cobalt manganese aluminum complex. Further, the nickel source may be selected from at least one of a hydroxide, a carbonate, and an oxalate of a nickel-containing metal.
The alkali metal compound includes at least a lithium compound. The content of the lithium compound is preferably 50-100 wt%. The lithium compound is selected from at least one of lithium hydroxide, lithium acetate, lithium nitrate, lithium sulfate and lithium bicarbonate. The alkali metal compound may contain 0 to 50 wt% of at least one of a potassium compound, a sodium compound, and a magnesium compound in addition to 50 to 100 wt% of a lithium compound. Specific examples of the potassium compound include, but are not limited to: at least one of potassium hydroxide, potassium acetate, potassium nitrate, potassium sulfate, and potassium bicarbonate. Specific examples of the sodium compound include, but are not limited to: at least one of sodium hydroxide, sodium acetate, sodium nitrate, sodium sulfate and sodium bicarbonate. Specific examples of the magnesium compound include, but are not limited to: at least one of magnesium chloride, magnesium hydroxide, magnesium acetate, magnesium nitrate, magnesium sulfate, and magnesium bicarbonate.
In the present invention, the oxidizing agent is at least one selected from hydrogen peroxide, manganate, and chlorate. Among them, the manganate is preferably potassium permanganate. The chlorate salt is preferably sodium chlorate and/or potassium chlorate.
In the invention, the additive has the functions of improving the lithium intercalation reaction rate and providing doping elements to change the crystal structure of the lithium intercalation nickel-containing metal oxide, thereby being more beneficial to improving the capacity retention rate of the lithium ion battery. The additive is preferably selected from at least one of titanium, aluminum, magnesium, zirconium, tungsten, yttrium, tantalum, niobium metal compounds, for example, hydroxides, oxides, salts thereof and the like of the above metals may be mentioned, and specific examples thereof include, but are not limited to: at least one of titanium oxide, aluminum hydroxide, magnesium oxide, zirconium oxide, ammonium tungstate, tungsten oxide, yttrium oxide, tantalum oxide, niobium oxide, and the like.
In a preferred embodiment, the molar ratio of nickel, oxidant, water and additive in the nickel-containing precursor is 1 (0.5-4): 0-0.2.
In a preferred embodiment, the molar ratio of Li/Ni of the nickel-containing precursor and the alkali metal compound is (0.9-1.3): 1.
In the present invention, in step S1, the nickel source is converted into a loose amorphous oxide after being pre-sintered. The temperature of the pre-sintering is 200 to 500 ℃, for example, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃ and the like; the sintering time is 2 to 10 hours, and for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, and the like may be used. The atmosphere for the pre-sintering is an oxidizing atmosphere, and for example, may be an air atmosphere, an oxygen atmosphere, or a mixed atmosphere of air and/or oxygen and an inert gas and/or a reducing gas. The inert gas may be, for example, nitrogen, argon, or the like. The reducing gas may be, for example, hydrogen.
In the present invention, in step S2, during the lithium intercalation reaction, the low valence metal such as Ni in the nickel-containing precursor2+Oxidized to a high valence state while lithium is pre-intercalated into the material. In a preferred embodiment, the conditions of the lithium intercalation reaction include a reaction temperature of 20 to 90 ℃ (i.e., the reaction temperature may be set to be within the range ofThe reaction temperature is normal temperature such as 20-35 ℃, or high temperature such as 35-90 ℃), the reaction pressure is 0.1-50 MPa (normal pressure can be 0.1MPa, or high pressure can be adopted), the concentration of alkali metal ions in the reaction system is 0.1-6 mol/L, and the stirring intensity is 0.1-1.6 kw/m2H, the reaction time is 3-60 h. In the present invention, the pressures are all absolute pressures.
In a preferred embodiment, the calcination conditions include a calcination temperature of 200 to 900 ℃, a calcination time of 1 to 40 hours, and a calcination atmosphere of air or oxygen.
In the present invention, the lithium intercalation reaction may be a batch reaction or a continuous reaction.
The invention also provides the lithium intercalation nickel-containing metal oxide prepared by the method.
In addition, the invention also provides application of the lithium-intercalated nickel-containing metal oxide as a lithium ion battery positive electrode material.
The lithium-intercalated nickel-containing metal oxide obtained by the method provided by the invention is used as a lithium ion battery anode material, so that the first discharge capacity and the capacity retention rate of the lithium ion battery can be obviously improved.
Drawings
FIGS. 1 and 2 are SEM images of the nickel-containing precursor obtained in example 1, wherein the magnification of FIG. 1 is 1k, and the magnification of FIG. 2 is 4 k;
FIGS. 3 and 4 are SEM images of the lithium-intercalated nickel-containing metal oxide obtained in example 1, wherein the magnification of FIG. 3 is 4k and the magnification of FIG. 4 is 8 k.
Detailed Description
The present invention will be described in detail below by way of examples.
Example 1
S1, pre-sintering the nickel-cobalt-manganese composite carbonate (the molar ratio of nickel to cobalt to manganese is 1:1:1) at 250 ℃ for 6 hours in an oxygen atmosphere to obtain a nickel-containing precursor. The scanning electron micrograph of the nickel-containing precursor is shown in fig. 1 and 2. As can be seen from fig. 1 and 2, the nickel-containing precursor is spheroidal.
S2, adding the obtained nickel-containing precursor (calculated by nickel, the same below) and lithium hydroxide, hydrogen peroxide, high-purity water and aluminum hydroxide into a reactor according to the molar ratio of 10:3:8:20:0.1 to perform lithium intercalation reaction so as to enable alkali metal ions to be intercalated into the nickel-containing precursor to form solid solution metal salt, controlling the lithium ion concentration to be 3.0mol/L by supplementing lithium hydroxide under the normal pressure condition, controlling the reaction temperature to be 60 ℃, and stirring the input power to be 0.7kw/m3H, adopting a continuous reaction form, keeping the material in the reactor for 15h, carrying out solid-liquid separation after the lithium intercalation reaction is finished, and then calcining the obtained solid product at 740 ℃ for 12 hours in an air atmosphere to obtain the lithium intercalation nickel-containing metal oxide with Li/Me of 1.08, which is recorded as QN 1. The scanning electron micrograph of the lithium-intercalated nickel-containing metal oxide QN1 is shown in FIGS. 3 and 4. As can be seen from fig. 3 and 4, the morphology of the lithium intercalation nickel-containing metal oxide QN1 is uniform in primary particle distribution.
Example 2
S1, pre-sintering nickel-cobalt-manganese composite oxalate (the molar ratio of nickel to cobalt to manganese is 5:2:3) at 200 ℃ for 10 hours in an oxygen atmosphere to obtain a nickel-containing precursor.
S2, adding the obtained nickel-containing precursor, lithium acetate, sodium chlorate, high-purity water and zirconia into a reactor according to the molar ratio of 10:4:7:15:0.04 to perform lithium intercalation reaction so as to enable alkali metal ions to be intercalated into the nickel-containing precursor to form solid solution metal salt, controlling the concentration of the lithium ions to be 5.0mol/L by supplementing lithium hydroxide under the condition of high pressure of 3.5MPa, controlling the reaction temperature to be 210 ℃, and controlling the stirring input power to be 0.3kw/m3H, adopting a batch reaction mode, keeping the material in the reactor for 20h, performing solid-liquid separation after the lithium intercalation reaction is finished, and calcining the obtained solid product at 890 ℃ for 18 hours in an air atmosphere to obtain the lithium intercalation nickel-containing metal oxide with Li/Me of 1.05, which is recorded as QN 2.
Example 3
S1, pre-sintering the nickel cobalt salt composite hydroxide (the molar ratio of nickel to cobalt is 4:1) for 2 hours at 300 ℃ in an oxygen atmosphere to obtain a nickel-containing precursor.
S2, mixing the obtained nickel-containing precursor with an alkali metal compound (lithium acetate and lithium hydroxide in a molar ratio of 1:1)) Adding an oxidant (sodium chlorate and potassium permanganate are mixed according to a molar ratio of 1:1), high-purity water and an additive (yttrium oxide and ammonium tungstate are mixed according to a molar ratio of 1:1) into a reactor according to a molar ratio of 10:5:11:20:0.05 to carry out lithium intercalation reaction so as to ensure that alkali metal ions are intercalated into a nickel-containing precursor to form solid solution metal salt, controlling the concentration of the lithium ions to be 2.0mol/L by supplementing lithium hydroxide under the condition of high pressure of 2.5MPa, controlling the reaction temperature to be 160 ℃, and stirring the input power to be 0.2kw/m3H, adopting a batch reaction form, keeping the material in the reactor for 30h, performing solid-liquid separation after the lithium intercalation reaction is finished, and calcining the obtained solid product at 860 ℃ for 18 hours in an air atmosphere to obtain the lithium intercalation nickel-containing metal oxide with Li/Me of 1.04, which is recorded as QN 3.
Example 4
S1, pre-sintering the nickel-cobalt-aluminum composite carbonate (the molar ratio of nickel to cobalt to aluminum is 8:1:1) at 250 ℃ for 6 hours in an oxygen atmosphere to obtain a nickel-containing precursor.
S2, adding the obtained nickel-containing precursor, lithium hydroxide, hydrogen peroxide, high-purity water and an additive (titanium oxide and magnesium oxide are mixed according to a molar ratio of 1:1) into a reactor according to a molar ratio of 10:5:11:10:0.05 to carry out lithium intercalation reaction so as to enable alkali metal ions to be intercalated into the nickel-containing precursor to form solid solution metal salt, controlling the lithium ion concentration to be 6.0mol/L by supplementing lithium hydroxide under the normal pressure condition, and stirring the input power to be 0.7kw/m3H, the reaction temperature is 60 ℃, a batch reaction mode is adopted, the material stays in the reactor for 20h, solid-liquid separation is carried out after the lithium intercalation reaction is finished, and then the obtained solid product is calcined at 820 ℃ for 18 h under the air atmosphere to obtain the lithium intercalation nickel-containing metal oxide with Li/Me of 1.04, which is recorded as QN 4.
Example 5
A lithium intercalating nickel containing metal oxide was prepared according to the procedure of example 1, except that no additive aluminum hydroxide was added during the lithium intercalation reaction, and the same procedure as in example 1 was followed to provide a lithium intercalating nickel containing metal oxide having Li/Me of 1.08, which was designated as QN 5.
Comparative example 1
A lithium intercalation nickel-containing metal oxide was prepared as in example 1, except that a pre-sintering step was not included, but the nickel-cobalt-manganese complex carbonate was directly charged into a reactor with lithium hydroxide, hydrogen peroxide, high purity water and aluminum hydroxide in a molar ratio of 10:3:8:20:0.1 for lithium intercalation reaction, and the rest of the conditions were the same as in example 1 to give a reference lithium intercalation nickel-containing metal oxide, designated DN1, with Li/Me ═ 1.08.
Comparative example 2
A lithium-intercalated nickel-containing metal oxide was prepared according to the method of example 1, except that step S2 was performed as follows: the nickel-containing precursor and lithium hydroxide are stirred and mixed uniformly, and then calcined for 12 hours at 740 ℃ in an air atmosphere, so that the reference lithium intercalation nickel-containing metal oxide with Li/Me of 1.08 is finally obtained and is recorded as DN 2.
Test example
The lithium-intercalated nickel-containing metal oxides QN 1-QN 5 obtained in examples 1-5 and the reference lithium-intercalated nickel-containing metal oxides DN 1-DN 2 obtained in comparative examples 1-2 are used as anode materials, and the anode materials, conductive carbon black and polyvinylidene fluoride (PVDF) are dissolved in an NMP solvent according to the mass ratio of 80:10:10 under the vacuum condition to prepare anode slurry with the solid content of 70 weight percent. And coating the positive electrode slurry on a current collector aluminum foil, drying at 120 ℃ in vacuum for 12h, and punching to obtain a positive electrode wafer with the diameter of 19 mm. Graphite, CMC and SBR are dissolved in deionized water according to the mass ratio of 90:5:5 under the vacuum condition to prepare negative pole slurry with the solid content of 40 weight percent. And coating the negative electrode slurry on a current collector copper foil, drying at 100 ℃ in vacuum for 12h, and punching to obtain a negative electrode wafer with the diameter of 19mm, wherein the negative electrode capacity and the positive electrode capacity are 1.1: 1. The battery is assembled in a glove box filled with argon for operation, the assembly sequence is sequentially a positive electrode shell, a positive electrode sheet, a diaphragm, a negative electrode sheet, a stainless steel sheet, a spring sheet and a negative electrode shell, the electrolyte is 1mol/L LiPF6/EC: DMC (volume ratio of 1:1) added with 10% (volume fraction) fluoroethylene carbonate (FEC), the diaphragm is a polypropylene microporous membrane, and the lithium ion battery C1-C5 and the reference lithium ion battery DC1-DC2 are obtained. The first discharge capacity and capacity retention rate of the lithium ion batteries C1-C5 and the reference lithium ion batteries DC1-DC2 were tested, and the obtained results are shown in Table 1.
TABLE 1
The results in table 1 show that the lithium-intercalated nickel-containing metal oxide prepared by the method provided by the invention can effectively improve the first discharge capacity and the capacity retention rate of the lithium ion battery when being used as the positive electrode material of the lithium ion battery, and has great industrial application prospects.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. A method of making a lithium intercalation nickel-containing metal oxide, the method comprising:
s1, pre-sintering a nickel source at 200-500 ℃ for 2-10 hours in an oxidizing atmosphere to obtain a nickel-containing precursor;
s2, mixing the nickel-containing precursor with an alkali metal compound, an oxidant, water and optional additives, and then carrying out lithium intercalation reaction, wherein the alkali metal compound at least comprises a lithium compound, so that alkali metal ions are intercalated into the nickel-containing precursor to form solid solution metal salt, carrying out solid-liquid separation after the lithium intercalation reaction is finished, and calcining the obtained solid product to obtain the lithium-intercalated and nickel-containing metal oxide.
2. The method of claim 1, wherein the metal elements of the nickel source include nickel and at least one of cobalt, manganese, and aluminum; the nickel source is selected from at least one of a hydroxide, a carbonate and an oxalate of a nickel-containing metal.
3. The method of claim 1, wherein the alkali metal compound comprises 50 to 100 wt% of a lithium compound and 0 to 50 wt% of at least one of a potassium compound, a sodium compound, and a magnesium compound; the lithium compound is selected from at least one of lithium hydroxide, lithium acetate, lithium nitrate, lithium sulfate and lithium bicarbonate, the potassium compound is selected from at least one of potassium hydroxide, potassium acetate, potassium nitrate, potassium sulfate and potassium bicarbonate, the sodium compound is selected from at least one of sodium hydroxide, sodium acetate, sodium nitrate, sodium sulfate and sodium bicarbonate, and the magnesium compound is selected from at least one of magnesium chloride, magnesium hydroxide, magnesium acetate, magnesium nitrate, magnesium sulfate and magnesium bicarbonate.
4. The method of claim 1, wherein the oxidant is at least one selected from hydrogen peroxide, manganate and chlorate; the manganate is preferably potassium permanganate; the chlorate salt is preferably sodium chlorate and/or potassium chlorate.
5. The method of claim 1, wherein the additive is at least one selected from the group consisting of titanium, aluminum, magnesium, zirconium, tungsten, yttrium, tantalum, and niobium metal compounds.
6. The method of claim 1, wherein the molar ratio of nickel, oxidant, water and additive in the nickel-containing precursor is 1 (0.5-4): 0-0.2; the molar ratio of Li/Ni of the nickel-containing precursor to alkali metal compound is (0.9-1.3): 1.
7. The method of claim 1, wherein the conditions of the lithium intercalation nickel-containing metal oxide include a reaction temperature of 20 to 90 ℃, a reaction pressure of 0.1 to 50MPa, an alkali metal ion concentration of 0.1 to 6mol/L in the reaction system, and a stirring intensity of 0.1 to 1.6kw/m of input power2H, the reaction time is 3-60 h.
8. The method of claim 1, wherein the calcining conditions include a calcining temperature of 200 to 900 ℃, a calcining time of 1 to 40 hours, and an air atmosphere or an oxygen atmosphere.
9. A lithium-intercalating nickel-containing metal oxide made by the method of any one of claims 1-8.
10. Use of the lithium-intercalating nickel-containing metal oxide of claim 9 as a positive electrode material for lithium ion batteries.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115432749A (en) * | 2022-10-10 | 2022-12-06 | 西北工业大学 | Pre-oxidation treated nickel-based positive electrode material and preparation method and application thereof |
| CN115536078A (en) * | 2022-10-10 | 2022-12-30 | 宁波容百新能源科技股份有限公司 | Lithium metal oxide precursor and preparation method and application thereof |
| CN115676917A (en) * | 2022-11-16 | 2023-02-03 | 宁波容百新能源科技股份有限公司 | Lithium-containing metal oxide precursor, preparation method thereof and lithium battery positive electrode material |
| CN116443951A (en) * | 2023-04-28 | 2023-07-18 | 厦门厦钨新能源材料股份有限公司 | Sodium-embedded lithium ion battery positive electrode material and preparation method thereof |
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| CN116443951A (en) * | 2023-04-28 | 2023-07-18 | 厦门厦钨新能源材料股份有限公司 | Sodium-embedded lithium ion battery positive electrode material and preparation method thereof |
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