CN109455773B - High-nickel ternary cathode material of lithium ion battery and preparation method thereof - Google Patents
High-nickel ternary cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN109455773B CN109455773B CN201811450582.8A CN201811450582A CN109455773B CN 109455773 B CN109455773 B CN 109455773B CN 201811450582 A CN201811450582 A CN 201811450582A CN 109455773 B CN109455773 B CN 109455773B
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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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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Abstract
The invention relates to a high-nickel ternary cathode material of a lithium ion battery and a preparation method thereof, wherein the chemical formula of the material is LiNixCoyMnzO2Wherein x is more than or equal to 0.5 and less than 1, and x + y + z is 1; the preparation method comprises the steps of weighing nickel nitrate and a surfactant according to a ratio, adding the nickel nitrate and the surfactant into a mixed solution of ethanol and water, adding urea, stirring, and transferring the mixture into a reaction kettle to perform hydrothermal reaction to obtain a suspension; cooling, filtering, washing and drying the suspension to obtain Ni (OH)2A precursor; reacting Ni (OH)2Adding the precursor, a manganese source and a cobalt source into the solution, mixing, then adding a lithium source to obtain a mixed solution, and evaporating the solvent to dryness to obtain a mixture solid; and sintering, cooling and grinding the mixture solid to obtain the cathode material. Compared with the prior art, the method has the advantages of simple preparation process, inhibition of nickel-lithium mixed-discharge phenomenon, excellent cycling stability and rate capability of the prepared cathode material and the like.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a high-nickel ternary cathode material of a lithium ion battery and a preparation method thereof.
Background
With exhaustion of fossil energy and increasingly serious environmental problems, people need to find novel energy storage materials to solve the problems faced at present. The lithium ion battery is a common secondary battery, and has the advantages of recycling, long service life, high energy density and the like, so that the lithium ion battery becomes a chemical energy storage device with the highest commercialization degree at present. At present, lithium ion batteries are widely applied to various fields of human life, such as mobile phones, computers, medical instruments and various small electronic devices, and are expected to be widely applied to large energy storage devices such as power automobiles and the like.
In lithium ion batteries, the specific capacity of the positive electrode material is generally low, which greatly determines the performance of the entire battery. And the cathode materials currently commercialized in the market include LiCoO2、LiFePO4And the like also have a problem of low specific capacity. And LiCoO2The price is high, and the toxicity is certain; LiFePO4The conductivity is poor, and the requirements of large energy storage equipment such as power automobiles and the like on high energy density and high power of batteries at present cannot be met. In recent years, ternary materials have been rapidly developed due to their advantages of low price, high specific capacity, good safety, etc. The ternary material can be classified into 111, 442, 523, 622, 811 and other types according to the molar ratio of nickel, cobalt and manganese elements in the ternary material. Along with the increase of the content of nickel, the specific capacity of the nickel is increased, the price is reduced, but the problems of serious nickel-lithium mixed discharge, excessive surface residual alkali and the like can be caused by too much content of nickel; the increase of the content of cobalt can improve the conductivity and rate capability of the material, but also can improve the cost and generate larger toxicity; the increased content of manganese can improve the safety of the material and stabilize the structure of the material, but the manganese can not provide a large capacity for the material. The requirements of the current market on the lithium ion battery anode material are more biased to high energy density and safety, so that the improvement of the nickel content in the ternary material is a simple and effective measure, and the preparation of the high-nickel ternary material with high cycle stability and excellent rate performance is always the key point of research of people.
Many modification methods such as doping, cladding, etc. have been proposed to address the shortcomings of high nickel ternary materials, but for pure phases they are generally prepared by hydroxide co-precipitation combined with high temperature solid phase sintering. In the process of hydroxide coprecipitation, because the bivalent manganese is easily oxidized into tetravalent manganese by air and exists in the precursor, the crystal structure of the precursor is influenced, and the performance of the sintered material is influenced, so that inert gas needs to be introduced for protection in the preparation process of the precursor, and the preparation difficulty and batch stability are obviously increased by the step. Researchers have also proposed many methods for making ternary materials, but further improvements are still needed to improve their cycling stability and rate capability.
Chinese patent CN108206279A discloses a high-nickel ternary positive electrode material of a lithium ion battery, and the chemical general formula is LiNixM1-xO2Wherein x is more than or equal to 0.5 and less than 1, M is one or more of Co, Mn and Al, the surface of the high-nickel ternary cathode material of the lithium ion battery is coated with a lithium salt coating layer, and the lithium salt is a lithium salt containing-COOLi functional groups. The method has the advantages that residual lithium on the surface of the high-nickel material is modified to form a stable lithium salt coating layer, so that residual lithium on the surface can be removed and coated on the surface of the material to form a protective layer, the generation of lithium carbonate can be inhibited, and the crystal structure of the material cannot be damaged; however, the patent only carries out surface residual alkali treatment on the homogeneous phase lithium ion battery high-nickel ternary positive electrode material prepared by a coprecipitation method, and does not fundamentally improve the nickel-lithium mixed-discharging phenomenon of the high-nickel ternary material. Moreover, the treating agent adopted in the patent has certain limitation, and the treating agent with too high acidity can damage the crystal structure of the material and can also aggravate nickel-lithium mixed discharge. Therefore, the direct solution of nickel-lithium mixed discharge from the synthetic route is also an important method for further improving the electrochemical performance of the material.
Therefore, under the condition of improving the nickel content, the mixed discharge of nickel and lithium is avoided, and the positive electrode material with high stability and better rate performance is obtained, so that the method has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-nickel ternary cathode material of a lithium ion battery and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a high-nickel ternary cathode material of a lithium ion battery comprises the following steps:
(1) adding nickel nitrate and a surfactant into a mixed solution of ethanol and water, adding urea, stirring, and transferring to a reaction kettle for hydrothermal reaction to obtain a suspension;
(2) cooling, filtering, washing and drying the suspension obtained in the step (1) to obtain Ni (OH)2A precursor;
(3) the Ni (OH) obtained in the step (2)2And mixing the precursor, the manganese source and the cobalt source in a liquid phase, adding the lithium source, drying and grinding the obtained mixed solution, and sintering, cooling and grinding the obtained solid to obtain the high-nickel ternary cathode material for the lithium ion battery.
When preparing the high-nickel cathode material, Ni is used2+Is difficult to be completely oxidized into Ni3+Thus prepared Ni-containing3+The positive electrode material (2) usually contains a certain amount of Ni2+. Due to Ni2+Radius and Li+The radii are very close, so Ni is in the material2+Possibly occupying Li+Position, and Li+May occupy Ni2+Thereby generating a nickel-lithium mixed-row phenomenon, so that the invention prepares Ni (OH) assembled by nanosheets with large specific surface area by using a hydrothermal method2The precursor has a larger contact area with oxygen in the lithium mixing and sintering process, so that divalent nickel can be more oxidized into trivalent nickel, the content of the divalent nickel is relatively reduced, and the divalent nickel occupying the lithium position is reduced, so that the nickel-lithium mixing and discharging phenomenon is reduced while the high-nickel ternary material is synthesized.
The surfactant in the step (1) is selected from one or more of CTAB, SDS or SDBS.
The molar ratio of the urea to the nickel nitrate in the step (1) is 3-10; the molar weight of the surfactant is 5-15% of that of the nickel nitrate.
The reaction temperature of the hydrothermal reaction in the step (1) is 110-130 ℃, and the reaction time is 12-18 h.
The cobalt source in the step (3) is selected from C4H6CoO4·4H2O、CoCl2·6H2O or CoSO4·7H2One or more of O.
The manganese source in the step (3) is selected from C4H6MnO4·4H2O、MnCl2·6H2O or MnSO4·4H2And O is one of the groups.
The lithium source in the step (3) is selected from LiOH & H2O、C2H3O2Li·2H2O or Li2CO3One or more of (a).
The solvent of the mixed solution in the step (3) is one or a mixture of more of deionized water, methanol and ethanol; the solvent is used in an amount to dissolve the solute.
The sintering treatment in the step (3) is specifically as follows: transferring the mixture solid into a tube furnace, heating to 500-550 ℃ at the heating rate of 2-4 ℃/min, and preserving heat for 5.5-6.5 h; then the temperature is raised to 750 ℃ and 900 ℃, and the temperature is kept for 14-16 h.
The high-nickel ternary cathode material for the lithium ion battery is prepared by the method, and has a chemical formula of LiNixCoyMnzO2Wherein x is more than or equal to 0.5 and less than 1, and x + y + z is 1.
The lithium ion battery high-nickel ternary cathode material is Ni (OH) prepared by a hydrothermal method2Is prepared for the precursor. Wherein the selection of the surfactant helps to form spherical Ni (OH) with regular morphology2It was found through experiments that Ni (OH) prepared using CTAB as a surfactant2The particle size distribution and the appearance are more uniform, so the particle size of the sintered material is more uniform, and the Ni (OH) prepared by taking SDS and SDBS as surfactants2The particle size is not as uniform as with CTAB, which affects the particle size distribution and uniformity of electrochemical performance of the sintered material. The dosage of the urea is in a certain range, and experiments show that when the dosage of the urea is too much (the molar ratio of the urea to the nickel nitrate is more than 10:1) or too little (the molar ratio of the urea to the nickel nitrate is less than 3:1), the synthesized Ni (OH) which is not a single crystal phase2And other impurities are contained, and the influence is generated on the finally synthesized high-nickel ternary cathode material. When ureaWhen the addition amount of (A) is within a certain range, the solvent in the reaction kettle is in a high-temperature and high-pressure environment, and the reaction pressure in the reaction kettle is influenced by different urea amounts, so that Ni (OH) with different shapes and different specific surface areas is generated2. In the present invention, we have found that the alloy is composed of Ni (OH) having a large specific surface area2The prepared high-nickel ternary material has the highest nickel oxidation degree and the lowest nickel-lithium mixed-out degree, which is the key influencing the electrochemical cycling stability and rate capability of the material.
Compared with the prior art, the invention utilizes Ni (OH)2The precursor is used for preparing the high-nickel ternary cathode material of the lithium ion battery, and the prepared material has excellent cycle and rate performance.
Firstly, the invention adopts a hydrothermal method to prepare Ni (OH)2The precursor avoids the steps of introducing inert gas for protection, adjusting pH, aging and the like in the process of preparing the precursor by the traditional hydroxide coprecipitation method, so that the preparation process is simpler;
secondly, hydrothermal preparation of Ni (OH)2The precursor is a flower-shaped structure assembled by nano sheets, and has a large specific surface area, so that the precursor is more easily oxidized into required positive trivalent nickel in the process of mixed sintering, and the phenomenon of mixed discharge of nickel and lithium is further inhibited;
finally, compared with the reported pure-phase ternary cathode material, the prepared high-nickel ternary cathode material has more excellent cycle stability and rate capability. The high-nickel ternary cathode material of the lithium ion battery prepared by the method is subjected to charge and discharge tests at 0.2 ℃, the charge range is 2.8-4.3V, and the maximum specific discharge capacity reaches 199.5mA h g-1After 60 times of charge and discharge, the capacity retention rate can reach 98 percent at most, and in a variable rate charge and discharge test, the maximum discharge capacity at 5C reaches 170mA h g-1And has excellent rate performance.
Drawings
FIG. 1 is an XRD pattern of the high nickel ternary positive electrode material of the lithium ion battery in examples 1-5;
FIG. 2 shows Ni (OH) composed of nanosheets in examples 1-32A precursor SEM image and an SEM image of a high-nickel ternary cathode material of the lithium ion battery;
FIG. 3 is a graph of the cycle performance at 0.2C for the high nickel ternary positive electrode material of the lithium ion batteries of examples 1-3;
FIG. 4 is a graph of rate capability of the high nickel ternary positive electrode material of the lithium ion batteries of examples 1-3;
in FIG. 2, a represents Ni (OH) composed of nanosheets in example 12SEM image of precursor, b is Ni (OH) composed of nanosheets in example 22SEM image of precursor, c is Ni (OH) composed of nanosheets in example 32A SEM image of the precursor, d is a SEM image of the lithium ion battery high nickel ternary cathode material in example 1, e is a SEM image of the lithium ion battery high nickel ternary cathode material in example 2, and f is a SEM image of the lithium ion battery high nickel ternary cathode material in example 3.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
In the following embodiments, the specific steps of applying the prepared high-nickel ternary cathode material for a lithium ion battery to battery assembly are as follows:
(1) preparing the obtained high-nickel ternary cathode material of the lithium ion battery into a pole piece:
mixing a high-nickel ternary positive electrode material, PVDF and acetylene black according to a mass ratio of 8:1:1, using N-methylpyrrolidone (NMP) as a solvent, uniformly stirring by using a ball mill to prepare coating slurry, quickly and uniformly coating the coating slurry on an aluminum foil, and drying in a vacuum drying oven at 110 ℃ for 12 hours in vacuum.
(2) A solution of 1MLiPF6 uniformly dispersed in an organic solvent (EMC (methyl ethyl carbonate) + EC (ethylene carbonate) + DMC (dimethyl carbonate)) is used as an electrolyte, the volume ratio of the three organic solvents is 1:1:1, a metal lithium sheet is used as a negative electrode sheet, a Celgard 2400 polyethylene film is used as a diaphragm, the three organic solvents are sequentially assembled into a button cell, and the button cell is stood for a period of time until the electrolyte is completely soaked for electrochemical test.
Example 1
A high nickel ternary positive electrode material of lithium ion battery, namely Ni (OH)2The chemical formula of the high-nickel ternary cathode material prepared by the precursor is LiNi0.8Co0.1Mn0.1O2，
The preparation method of the high-nickel ternary cathode material for the lithium ion battery specifically comprises the following steps:
(1) hydrothermal preparation of Ni (OH)2Precursor (chemical formula Ni (OH))2·0.75H2O) step:
weighing 1.57g of nickel nitrate and 0.25g of CTAB, dissolving in a mixed solvent (50ml) of water and ethanol in a volume ratio of 1:1, uniformly stirring, adding 0.9g of urea, continuously uniformly stirring, transferring to a 100ml reaction kettle, preserving heat at 120 ℃ for 15h, naturally cooling to room temperature after heat preservation is finished, washing and filtering the precipitate, and finally drying in an air-blast drying box at 80 ℃.
(2) Preparation of LiNi by high-temperature solid-phase sintering0.8Co0.1Mn0.1O2The steps of (1):
weighing a certain amount of Ni (OH)2A precursor of the formula Ni (OH)2·0.75H2O, uniformly dispersing cobalt acetate and manganese acetate (Ni: Co: Mn: 8:1:1) in a certain molar ratio in the solution, adding a corresponding amount of lithium hydroxide monohydrate into the solution, uniformly mixing, heating to evaporate the solution to dryness, grinding into powder, placing the powder in a tube furnace to perform high-temperature sintering in an oxygen atmosphere at a heating rate of 3 ℃/min, heating to 530 ℃ and keeping the temperature for 6h, then heating to 800 ℃ and keeping the temperature for 15h, naturally cooling to room temperature after the heating is finished, grinding the obtained black powder, and finally obtaining the required LiNi0.8Co0.1Mn0.1O2。
Example 2
A high nickel ternary positive electrode material of lithium ion battery, namely Ni (OH)2The chemical formula of the high-nickel ternary cathode material prepared by the precursor is LiNi0.8Co0.1Mn0.1O2，
The preparation method of the high-nickel ternary cathode material for the lithium ion battery specifically comprises the following steps:
(1) hydrothermal preparation of Ni (OH)2Precursor (chemical formula Ni (OH))2·0.75H2O) step:
weighing 1.57g of nickel nitrate and 0.25g of CTAB, dissolving in a mixed solvent (50ml) of water and ethanol in a volume ratio of 1:1, uniformly stirring, adding 1.5g of urea, continuously uniformly stirring, transferring to a 100ml reaction kettle, preserving heat at 120 ℃ for 15h, naturally cooling to room temperature after heat preservation is finished, washing and filtering the precipitate, and finally drying in an air-blast drying box at 80 ℃.
(2) Preparation of high-nickel ternary positive electrode material (chemical formula LiNi) by high-temperature solid-phase sintering0.8Co0.1Mn0.1O2) The steps of (1):
weighing a certain amount of Ni (OH)2A precursor of the formula Ni (OH)2·0.75H2O, uniformly dispersing cobalt acetate and manganese acetate (Ni: Co: Mn: 8:1:1) in a certain molar ratio in a solution, adding a corresponding amount of lithium hydroxide monohydrate into the solution, uniformly mixing, heating to evaporate the solution to dryness, grinding into powder, placing the powder in a tube furnace to perform high-temperature sintering in an oxygen atmosphere at a heating rate of 3 ℃/min, heating to 530 ℃ and keeping the temperature for 6h, then heating to 800 ℃ and keeping the temperature for 15h, naturally cooling to room temperature after the heating is finished, grinding the obtained black powder, and finally obtaining the required high-nickel ternary cathode material (chemical formula LiNi)0.8Co0.1Mn0.1O2)。
Example 3
A high nickel ternary positive electrode material of lithium ion battery, namely Ni (OH)2The chemical formula of the high-nickel ternary cathode material prepared by the precursor is LiNi0.8Co0.1Mn0.1O2，
The preparation method of the high-nickel ternary cathode material for the lithium ion battery specifically comprises the following steps:
(1) hydrothermal preparation of Ni (OH)2Precursor (chemical formula Ni (OH))2·0.75H2O) step:
weighing 1.57g of nickel nitrate and 0.25g of CTAB, dissolving in a mixed solvent (50ml) of water and ethanol in a volume ratio of 1:1, uniformly stirring, adding 2.7g of urea, continuously uniformly stirring, transferring to a 100ml reaction kettle, preserving heat at 120 ℃ for 15h, naturally cooling to room temperature after heat preservation is finished, washing and filtering the precipitate, and finally drying in an air-blast drying box at 80 ℃.
(2) Preparation of high-nickel ternary positive electrode material (chemical formula LiNi) by high-temperature solid-phase sintering0.8Co0.1Mn0.1O2) The steps of (1):
weighing a certain amount of Ni (OH)2A precursor of the formula Ni (OH)2·0.75H2O, uniformly dispersing cobalt acetate and manganese acetate (Ni: Co: Mn: 8:1:1) in a certain molar ratio in a solution, adding a corresponding amount of lithium hydroxide monohydrate into the solution, uniformly mixing, heating to evaporate the solution to dryness, grinding into powder, placing the powder in a tube furnace to perform high-temperature sintering in an oxygen atmosphere at a heating rate of 3 ℃/min, heating to 530 ℃ and keeping the temperature for 6h, then heating to 800 ℃ and keeping the temperature for 15h, naturally cooling to room temperature after the heating is finished, grinding the obtained black powder, and finally obtaining the required high-nickel ternary cathode material (chemical formula LiNi)0.8Co0.1Mn0.1O2)。
Example 4
A high nickel ternary positive electrode material of lithium ion battery, namely Ni (OH)2The chemical formula of the high-nickel ternary cathode material prepared by the precursor is LiNi0.8Co0.1Mn0.1O2，
The preparation method of the high-nickel ternary cathode material for the lithium ion battery specifically comprises the following steps:
(1) hydrothermal preparation of Ni (OH)2Precursor (chemical formula Ni (OH))2·0.75H2O) step:
weighing 1.57g of nickel nitrate and 0.25g of SDBS, dissolving in a mixed solvent (50ml) with a volume ratio of water to ethanol of 1:1, stirring uniformly, adding 0.9g of urea, continuously stirring uniformly, transferring to a 100ml reaction kettle, preserving heat at 120 ℃ for 15h, naturally cooling to room temperature after heat preservation is finished, washing and filtering the precipitate, and finally drying in an air-blast drying box at 80 ℃.
(2) Preparation of high-nickel ternary positive electrode material (chemical formula LiNi) by high-temperature solid-phase sintering0.8Co0.1Mn0.1O2) The steps of (1):
weighing a certain amount of Ni (OH)2A precursor of the formula Ni (OH)2·0.75H2O, uniformly dispersing cobalt acetate and manganese acetate (Ni: Co: Mn: 8:1:1) in a certain molar ratio in a solution, adding a corresponding amount of lithium hydroxide monohydrate into the solution, uniformly mixing, heating to evaporate the solution to dryness, grinding into powder, placing the powder in a tube furnace to perform high-temperature sintering in an oxygen atmosphere at a heating rate of 3 ℃/min, heating to 500 ℃ and keeping the temperature for 6h, then heating to 800 ℃ and keeping the temperature for 15h, naturally cooling to room temperature after the heating is finished, grinding the obtained black powder, and finally obtaining the required high-nickel ternary cathode material (chemical formula LiNi)0.8Co0.1Mn0.1O2)。
Example 5
A high nickel ternary positive electrode material of lithium ion battery, namely Ni (OH)2The chemical formula of the high-nickel ternary cathode material prepared by the precursor is LiNi0.8Co0.1Mn0.1O2，
The preparation method of the high-nickel ternary cathode material for the lithium ion battery specifically comprises the following steps:
(1) hydrothermal preparation of Ni (OH)2Precursor (chemical formula Ni (OH))2·0.75H2O) step:
weighing 1.57g of nickel nitrate and 0.25g of SDBS, dissolving in a mixed solvent (50ml) with a volume ratio of water to ethanol of 1:1, stirring uniformly, adding 1.5g of urea, continuously stirring uniformly, transferring to a 100ml reaction kettle, preserving heat at 120 ℃ for 15h, naturally cooling to room temperature after heat preservation is finished, washing and filtering the precipitate, and finally drying in an air-blast drying box at 80 ℃.
(2) Preparation of high-nickel ternary positive electrode material (chemical formula LiNi) by high-temperature solid-phase sintering0.8Co0.1Mn0.1O2) The steps of (1):
weighing a certain amount of Ni (OH)2A precursor of the formula Ni (OH)2·0.75H2O, uniformly dispersing cobalt acetate and manganese acetate (Ni: Co: Mn: 8:1:1) in a certain molar ratio in a solution, adding a corresponding amount of lithium hydroxide monohydrate into the solution, uniformly mixing, heating to evaporate the solution to dryness, grinding into powder, placing the powder in a tube furnace to perform high-temperature sintering in an oxygen atmosphere at a heating rate of 3 ℃/min, heating to 550 ℃, keeping the temperature for 6h, then heating to 800 ℃, keeping the temperature for 15h, naturally cooling to room temperature after the heating is finished, grinding the obtained black powder, and finally obtaining the required high-nickel ternary cathode material (chemical formula LiNi)0.8Co0.1Mn0.1O2)。
The high nickel ternary positive electrode material LiNi obtained in example 1 was subjected to X-ray diffractometry using a Bruker model D8ADVANCE X-ray diffractometer0.8Co0.1Mn0.1O2High nickel ternary positive electrode material LiNi obtained in example 20.8Co0.1Mn0.1O2(ii) a High nickel ternary positive electrode material LiNi obtained in example 30.8Co0.1Mn0.1O2(ii) a High nickel ternary positive electrode material LiNi obtained in example 40.8Co0.1Mn0.1O2And the high nickel ternary positive electrode material LiNi obtained in example 50.8Co0.1Mn0.1O2The XRD patterns obtained by the respective tests are shown in figure 1, and all the synthesized samples can be seen to have diffraction peaks with the same positions and small intensity, and compared with a standard PDF card, the obtained material has hexagonal system alpha-NaFeO of R3-m space group2The structure, in the XRD patterns of the samples obtained in all the examples, two pairs of splitting peaks (006)/(102) and (108)/(110) represent the integrity of the layered structure of the material, the intensity ratio of the peaks (003) and (104) represents the degree of nickel-lithium mixing, and the larger the intensity ratio of the peaks (003) and (104)The smaller the degree of cation misarrangement of the material. As can be seen from the figure, the splitting degree of the two-component splitting peaks of (006)/(102) and (108)/(110) is most apparent in example 1, and the intensity ratio of the (003) and (104) peaks is the largest, indicating that Ni (OH) prepared using the method of example 12The high nickel ternary material synthesized by the precursor has the best crystal structure.
The Ni (OH) obtained in examples 1, 2 and 3 was subjected to field emission scanning electron microscopy2Precursor and finally synthesized high-nickel ternary cathode material LiNi0.8Co0.1Mn0.1O2The SEM results are shown in FIG. 2(a, b, c), and the results of example 1, example 2 and example 3 are Ni (OH)2The particle sizes of the precursors are basically the same, and the precursors are all flower-shaped microspheres composed of nano sheets, wherein the flower-shaped microspheres in example 1 are composed of nano sheets which are closely packed, the flower-shaped microspheres in example 2 are composed of nano sheets which are connected with each other, and the flower-shaped microspheres in example 3 are composed of nano sheets which are connected sparsely. Ni (OH) synthesized in three examples2The structure of the precursor is obviously different, which causes the difference of the specific surface area, and Ni (OH) synthesized by three examples2The precursor was subjected to a specific surface area test to obtain Ni (OH) in example 12The specific surface area of the precursor is the largest, and the high-nickel ternary cathode material LiNi prepared in the embodiment 1, the embodiment 2 and the embodiment 3 is combined0.8Co0.1Mn0.1O2XRD of (B) showed that the powder had the largest specific surface area of Ni (OH)2High-nickel ternary positive electrode material LiNi synthesized by precursor0.8Co0.1Mn0.1O2The nickel-lithium mixed-out degree is lowest, and the formed crystal structure is best. This is due to the largest specific surface area of Ni (OH)2The precursor can have the largest contact area with oxygen in the sintering process after mixing the lithium source, the manganese source and the cobalt source. Thus, the high nickel ternary positive electrode material LiNi obtained in example 10.8Co0.1Mn0.1O2More divalent nickel can be oxidized into trivalent nickel in the sintering process, and the nickel-lithium mixed discharging degree is reduced to a certain extent. Nickel-lithium mixed-row ternary cathode material for high nickelThe material is a very important index, and the serious mixed discharging of nickel and lithium causes the material to have large irreversible capacity and the cycle performance to be poor, so that the inhibition of the mixed discharging of nickel and lithium of the high-nickel ternary material is a necessary way for improving the electrochemical performance of the material.
The high-nickel ternary cathode materials LiNi obtained in the embodiments 1, 2 and 3 are subjected to field emission scanning electron microscopy0.8Co0.1Mn0.1O2Tests were carried out, and as shown in fig. 2(d, e, f), the morphologies of the three particles in example 1, example 2 and example 3 were similar, which indicates that the morphology of the precursor composed of the nanosheets has no influence on the synthesized high-nickel ternary material. By reaction with Ni (OH)2Compared with the precursor, the particle diameters of the precursor synthesized in the embodiment 1, the embodiment 2 and the embodiment 3 are basically the same as that of the finally obtained high-nickel ternary cathode material, but the nano-sheet on the surface of the precursor is converted into irregular nano-particles in the sintering process.
The high nickel ternary positive electrode materials LiNi obtained in the above examples 1, 2 and 3 were used0.8Co0.1Mn0.1O2As the active material of the positive electrode material, the button cell is assembled by the battery slurry coating method and the button cell assembling method, finally, the test is carried out by using a LAND CT2001A battery test system of blue electronic corporation of Wuhan city, the temperature is controlled at 25 ℃, the charging and discharging range is 2.8-4.3V, the charging and discharging cycle result is shown in figure 3, the first discharging specific capacity is 194.9mA h g-1、199.5mA h g-1And 196.4mA h g-1The initial discharge specific capacities of the three materials are similar, but the capacity retention rates of the three materials are respectively 98%, 87.9% and 86.7% after 60 cycles. From these data, it can be seen that the high nickel ternary positive electrode material LiNi obtained in example 1, in which the degree of nickel-lithium intercalation is lowest, is obtained0.8Co0.1Mn0.1O2The cycling performance is best.
FIG. 4 shows LiNi, a high-nickel ternary positive electrode material obtained in example 1, example 2 and example 30.8Co0.1Mn0.1O2The multiplying power performance diagram of the test button cell is that all the button cells to be tested areIs assembled according to the method, the charging and discharging range is 2.8-4.6V, the charging is carried out at 0.2C, and the discharging is carried out at 0.2C, 0.5C, 1C, 2C, 5C and 0.2C in sequence, and as can be seen from figure 4, the high-nickel ternary cathode material LiNi obtained in example 1, example 2 and example 30.8Co0.1Mn0.1O2The first discharge specific capacity of the lithium ion battery is 216.2mA h g-1、216.7mA h g-1And 213.6mA h g-1When the multiplying power reaches 5C, the high-nickel ternary cathode materials LiNi obtained in the embodiments 1, 2 and 30.8Co0.1Mn0.1O2The specific discharge capacity is 170.9mA h g-1、155.4mA h g-1And 144.4mAh g-1When the current density returns to 0.2C, the high-nickel ternary cathode materials LiNi obtained in example 1, example 2 and example 30.8Co0.1Mn0.1O2The specific discharge capacity is 198.3mA h g-1、187.7mA h g-1And 194.7mA hr g-1. From the rate performance graph, it can be found that the high-nickel ternary cathode material LiNi obtained in example 10.8Co0.1Mn0.1O2When the current density reaches 5C at maximum, 170.9mA h g can be still kept-1The specific capacity and the current density returned to 0.2C, the discharge specific capacity was the highest, which indicates that the high nickel ternary positive electrode material LiNi obtained in example 1, which has the lowest degree of nickel-lithium mixing and discharging0.8Co0.1Mn0.1O2The rate capability is best.
According to the high-nickel ternary cathode material for the lithium ion battery, when the specific surface area of the prepared precursor is large, the nickel-lithium mixed-discharging degree of the synthesized high-nickel ternary cathode material is lower, and the cycle performance and the rate capability of the material are better.
Example 6
A high nickel ternary positive electrode material of lithium ion battery, namely Ni (OH)2The chemical formula of the high-nickel ternary cathode material prepared by the precursor is LiNi0.6Co0.2Mn0.2O2，
The preparation method of the high-nickel ternary cathode material for the lithium ion battery specifically comprises the following steps:
(1) hydrothermal preparation of Ni (OH)2Precursor (chemical formula Ni (OH))2·0.75H2O) step:
weighing 1.57g of nickel nitrate and 0.39g of SDS, dissolving in a mixed solvent (50ml) of water and ethanol in a volume ratio of 1:1, uniformly stirring, adding 3.27g of urea, continuously uniformly stirring, transferring to a 100ml reaction kettle, preserving heat at 110 ℃ for 18h, naturally cooling to room temperature after heat preservation is finished, washing and filtering the precipitate, and finally drying in an air-blast drying box at 80 ℃.
(2) Preparation of LiNi by high-temperature solid-phase sintering0.6Co0.2Mn0.2O2The steps of (1):
weighing a certain amount of Ni (OH)2A precursor of the formula Ni (OH)2·0.75H2O, and CoCl in a certain molar ratio2·6H2O and MnCl2·6H2O (Ni: Co: Mn: 6:2:2) was uniformly dispersed in the solution, and C was added to the solution in an amount corresponding to the amount of C2H3O2Li·2H2O, uniformly mixing, heating to evaporate the solution to dryness, grinding into powder, placing in a tube furnace for high-temperature sintering in an oxygen atmosphere, heating to 520 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 6.5h, then heating to 750 ℃ and keeping the temperature for 16h, naturally cooling to room temperature after finishing, grinding the obtained black powder to finally obtain the required LiNi0.6Co0.2Mn0.2O2。
Example 7
A high nickel ternary positive electrode material of lithium ion battery, namely Ni (OH)2The chemical formula of the high-nickel ternary cathode material prepared by the precursor is LiNi0.5Co0.3Mn0.2O2，
The preparation method of the high-nickel ternary cathode material for the lithium ion battery specifically comprises the following steps:
(1) hydrothermal preparation of Ni (OH)2Precursor (chemical formula Ni (OH))2·0.75H2O) step:
weighing 1.57g of nickel nitrate and 0.16g of CTAB, dissolving in a mixed solvent (50ml) of water and ethanol in a volume ratio of 1:1, uniformly stirring, adding 2.7g of urea, continuously uniformly stirring, transferring to a 100ml reaction kettle, preserving heat at 130 ℃ for 12h, naturally cooling to room temperature after heat preservation is finished, washing and filtering the precipitate, and finally drying in an air-blast drying box at 80 ℃.
(2) Preparation of LiNi by high-temperature solid-phase sintering0.5Co0.3Mn0.2O2The steps of (1):
weighing a certain amount of Ni (OH)2A precursor of the formula Ni (OH)2·0.75H2O, and a certain molar ratio of CoSO4·7H2O and MnSO4·4H2O (Ni: Co: Mn: 5:3:2) is uniformly dispersed in the solution, and a corresponding amount of Li is added to the solution2CO3Uniformly mixing, heating to evaporate the solution to dryness, grinding into powder, placing in a tubular furnace for high-temperature sintering in an oxygen atmosphere at a heating rate of 4 ℃/min, heating to 540 ℃, preserving heat for 5.5h, then heating to 950 ℃, preserving heat for 14h, naturally cooling to room temperature after finishing, grinding the obtained black powder to finally obtain the required LiNi0.5Co0.3Mn0.2O2。
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (9)
1. A preparation method of a high-nickel ternary cathode material of a lithium ion battery is characterized by comprising the following steps:
(1) adding nickel nitrate and a surfactant CTAB into a mixed solution of ethanol and water, adding urea, stirring, and transferring to a reaction kettle for hydrothermal reaction to obtain a suspension;
(2) cooling, filtering, washing and drying the suspension obtained in the step (1) to obtain Ni (OH)2A precursor;
(3) the Ni (OH) obtained in the step (2)2And mixing the precursor, the manganese source and the cobalt source in a liquid phase, adding the lithium source, drying and grinding the obtained mixed solution, and sintering, cooling and grinding the obtained solid to obtain the high-nickel ternary cathode material for the lithium ion battery.
2. The preparation method of the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the molar ratio of urea to nickel nitrate in the step (1) is 3-10; the molar weight of the surfactant is 5-15% of that of the nickel nitrate.
3. The method for preparing the high-nickel ternary cathode material for the lithium ion battery as claimed in claim 1, wherein the hydrothermal reaction in the step (1) is performed at a temperature of 110-.
4. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the cobalt source in the step (3) is selected from C4H6CoO4·4H2O、CoCl2·6H2O or CoSO4·7H2One or more of O.
5. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the manganese source in the step (3) is selected from C4H6MnO4·4H2O、MnCl2·6H2O or MnSO4·4H2And O is one of the groups.
6. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the lithium source in the step (3) is selected from LiOH. H2O、C2H3O2Li·2H2O or Li2CO3One or more of (a).
7. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the solvent of the mixed solution in the step (3) is one or more selected from deionized water, methanol and ethanol.
8. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the sintering treatment in the step (3) is specifically as follows: transferring the solid into a tube furnace, heating to 500-550 ℃ at a heating rate of 2-4 ℃/min, and preserving heat for 5.5-6.5 h; then the temperature is raised to 750 ℃ and 900 ℃, and the temperature is kept for 14-16 h.
9. The lithium ion battery high-nickel ternary cathode material prepared by the method of claim 1, wherein the chemical formula of the lithium ion battery high-nickel ternary cathode material is LiNixCoyMnzO2Wherein x is more than or equal to 0.5 and less than 1, and x + y + z is 1.
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