CN113889616A - High-tap-density lithium-rich manganese-based positive electrode material and preparation method thereof - Google Patents
High-tap-density lithium-rich manganese-based positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-tap-density lithium-rich manganese-based positive electrode material and a preparation method thereof. By simultaneously adding the boron-containing compound and the phosphorus-containing compound as fluxing agents in the preparation process of the lithium-rich manganese-based positive electrode material, the fluidity of the lithium-rich manganese-based material in the calcining process is improved through the synergistic fluxing action of boron and phosphorus, the fusion among primary particles is promoted, and the pores among the primary particles are reduced. The tap density of the lithium-rich manganese-based material prepared by the method can reach 2.3g/cm3The tap density of the lithium-rich manganese-based material is obviously improved on the premise of not sacrificing the capacity of the material and other electrochemical properties. The invention has simple process, less fluxing agent consumption and the preparation process of the precursorThe method has the advantages of no need of newly-added equipment, and suitability for large-scale production.
Description
Technical Field
The invention belongs to the field of lithium ion battery anode materials, and particularly relates to a high-tap-density lithium-rich manganese-based anode material and a preparation method thereof.
Background
With the development of energy storage and new energy automobile industry, the demand of lithium ion batteries is increasingly vigorous, however, the energy density of the lithium ion batteries at present cannot well meet the market demand, and the improvement of the energy density of the lithium ion batteries is urgent. The positive electrode material provides a lithium source in the lithium ion battery and determines the voltage of the lithium ion battery, thereby playing a key role in the performance of the lithium ion battery. Therefore, the development of the high-specific-capacity and high-voltage anode material is an effective section for improving the energy density of the lithium ion battery. Currently commercialized positive electrode materials such as LiCoO2、LiFePO4、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.15Al0.05O2The actual specific capacity is lower than 200mAh/g, and the space for further improving is narrow. The development of a novel positive electrode material with high specific capacity and high voltage becomes a necessary choice. The lithium-rich manganese-based positive electrode material has the characteristics of high specific capacity and low cost, and the chemical general formula of the material is Li [ Li ]aM1-a]O2(M ═ Ni, Co, Mn) (also written as xLiMO)2·(1-x)Li2MnO3M is Ni, Co and Mn), the theoretical specific discharge capacity exceeds 300mAh/g, the actual specific discharge capacity can reach more than 250mAh/g, the average discharge voltage is higher than 3.5V, and transition metal elements mainly adopt Mn with low cost, so that the lithium ion battery anode material is an ideal choice for the next generation of high-energy-density lithium ion batteries.
Although the lithium-rich manganese-based material has high specific discharge capacity, the tap density is lower (less than 1.8 g/cm)3) The volume energy density of the lithium-rich manganese-based material is not dominant compared with the existing high-nickel cathode material; in addition, the lower tap density is not favorable for the dispersion of the positive electrode material in an N-methyl pyrrolidone (NMP) solvent in the pole piece coating process. Therefore, the preparation of the lithium-rich manganese-based material with high tap density is very critical to the practical application of the material.
The tap density of the lithium-rich manganese-based material prepared by the coprecipitation method mainly depends on the tap density of the precursor, and because the manganese content in the lithium-rich manganese-based material is higher, when the precursor is prepared by adopting a hydroxide coprecipitation process, nucleation is too fast in the precipitation process, balling is not easy to control, and meanwhile, Mn is not easy to control2+The precursor is easy to be oxidized under an alkaline condition, so that the shape of the precursor is poor; the precursor prepared by adopting the carbonate coprecipitation process can generate a large amount of gas in the calcining process, so that the calcined structure becomes loose and high tap density is not easy to obtainA dense lithium rich manganese based material. In addition, the lithium-rich manganese-based material has a higher melting temperature, which is more unfavorable for obtaining a material with high tap density.
Disclosure of Invention
Aiming at the problem of low tap density of the lithium-rich manganese-based material, the invention provides a method for improving tap density by adding a fluxing agent. The fluxing agent is a substance capable of reducing the softening and melting temperature of the substance and has the function of promoting the growth of crystals. The addition of the flux improves the fluidity of the lithium-rich manganese-based material during calcination, promotes the fusion between primary particles, and thus reduces the pores between the primary particles. According to the invention, through the synergistic effect of the two fluxing agents of boron and phosphorus, the tap density of the lithium-rich manganese-based material is obviously improved on the premise of not sacrificing the capacity of the material and other electrochemical properties, so that the volume energy density of the corresponding battery is improved, and the practical process of the lithium-rich manganese-based material is promoted.
The scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a lithium-rich manganese-based positive electrode material of a high tap density lithium ion battery comprises the following steps:
a. mixing a lithium source, a nickel source, a cobalt source and a manganese source compound according to a stoichiometric ratio, adding a solvent, and uniformly grinding by using a ball milling or sanding mode to obtain uniform slurry;
b. adding a boron source compound and a phosphorus source compound into the obtained slurry, continuously grinding, and uniformly mixing;
c. drying the slurry obtained in the step b by using a spray dryer to obtain spherical precursor powder;
d. calcining the obtained precursor powder at high temperature: presintering at 400-500 ℃ for 1-6h, then heating to 800-1000 ℃ for calcining for 8-24h, cooling and crushing to obtain the target product.
Preferably, the chemical formula of the lithium-rich manganese-based cathode material is as follows: li [ Li ]xNiaCobMnc]O2，a+b+c+x＝1，0<a<1、0≤b<1，0<c<1，0<x≤0.33。
Preferably, in step a, the lithium source compound is selected from any one or more of lithium oxide, lithium carbonate, lithium nitrate, lithium hydroxide, lithium acetate and lithium oxalate; the nickel source compound is selected from any one or more of nickel oxide, nickel carbonate, basic nickel carbonate, nickel nitrate, nickel acetate and nickel oxalate; the manganese source compound is selected from any one or more of manganese dioxide, manganese sesquioxide, manganese monoxide, manganese carbonate, manganese nitrate, manganese acetate and manganese oxalate; the cobalt source compound is selected from any one or more of cobaltosic oxide, cobalt carbonate, cobalt nitrate, cobalt acetate and cobalt oxalate.
Preferably, in step a, the solvent is any one or a mixture of ethanol, water, acetone and N-methylpyrrolidone.
Preferably, in the step a, the solvent is ethanol, water, acetone N-methyl pyrrolidone, a mixed solvent of ethanol and water in a mass ratio of 1:1, or a mixed solvent of water and acetone in a mass ratio of 1: 1.
Preferably, in step a, the amount of solvent is added in the range of 10-50% solids.
Preferably, in step b, the boron source compound is selected from any one or more of diboron trioxide, borax, boric acid and lithium borate; the phosphorus source compound is selected from one or more of phosphorus pentoxide, ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate and potassium phosphate.
Preferably, in step b, the molar amount of boron element added accounts for the target product Li [ Li ]xNiaCobMnc]O20.1-5% of molar weight, and the molar weight of the added phosphorus element accounts for the target product Li [ ]xNiaCobMnc]O20.1-5% of the molar weight.
Preferably, the addition molar ratio of the boron element to the phosphorus element is 1: 1. More preferably, the addition amounts of the boron element and the phosphorus element are both 1%.
The invention also aims to provide a lithium-rich manganese-based positive electrode material of the high-tap-density lithium ion battery, which is prepared by adopting the preparation method.
Preferably, the positive electrode materialThe tap density of the steel can reach 2.1g/cm3Above, more preferably up to 2.3g/cm3The above.
The invention also aims to provide a lithium ion battery, wherein the positive electrode material of the lithium ion battery is the lithium-rich manganese-based positive electrode material with high tap density, or the lithium-rich manganese-based positive electrode material with high tap density prepared by the preparation method.
The method of the invention has the following remarkable effects:
1. the invention has the advantages that the dosage of the added fluxing agent is small, the achieved effect is very obvious, the tap density of the material can be greatly improved by adding the fluxing agent with the content of less than 5 percent, and the tap density can reach 2.3g/cm3The above;
2. the dosage of the added fluxing agent is small, so that the fluxing agent does not have negative influence on the electrochemical performance of the material;
3. the method is simple and reliable in process and suitable for large-scale production of the lithium-rich manganese-based positive electrode material with high tap density.
Drawings
Fig. 1 is an SEM image of the lithium-rich manganese-based material prepared in example 1, wherein the left and right images are images at different magnifications, respectively;
fig. 2 is an SEM image of the lithium-rich manganese-based material prepared in comparative example 1, wherein the left and right images are images at different magnifications, respectively;
fig. 3 is an SEM image of the lithium-rich manganese-based material prepared in comparative example 3, wherein the left and right images are images at different magnifications, respectively;
fig. 4 is an SEM image of the lithium-rich manganese-based material prepared in comparative example 4, wherein the left and right images are images at different magnifications, respectively;
fig. 5 is a first-cycle charge-discharge curve of the lithium-rich manganese-based materials prepared in example 1 and comparative example 1;
FIG. 6 is a graph showing the cycling performance of the lithium-rich manganese-based material prepared in example 1 at a current density of 100 mA/g.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
The present invention will be described in further detail with reference to examples and comparative examples. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration and explanation only and are not intended to limit the scope of the invention.
Example 1
According to Li1.15Ni0.28Mn0.57O2Adding lithium carbonate, nickel nitrate and manganese dioxide in stoichiometric ratio into a ball milling tank, adding a certain amount of mixed solvent of ethanol and water in a mass ratio of 1:1 according to 40% of solid content, ball milling for 6 hours, and then adding diboron trioxide and phosphorus pentoxide, wherein the molar weight of boron element accounts for Li1.15Ni0.28Mn0.57O21% of the molar amount of the phosphorus element in the Li1.15Ni0.28Mn0.57O2And (4) continuing ball milling for 1h according to the molar weight of 1%. And then drying the slurry by a spray dryer, calcining the obtained powder in a muffle furnace at 450 ℃ for 5h, heating to 900 ℃ for 12h, cooling, crushing and sieving to obtain the target product. The material is used as a positive electrode, a lithium sheet is used as a negative electrode, a button cell is assembled, and the electrochemical performance is tested, wherein the test voltage range is 2.0-4.8V, the current density is 0.1C (25mA/g), and the temperature is 25 ℃.
The SEM image of the target product is shown in FIG. 1, and it can be seen that the material particles are spherical, the particle size is about 5-30um, and the primary particles are tightly bonded. The tap density was found to be 2.35g/cm3. The electrochemical test result is shown in fig. 5, the first-cycle specific discharge capacity is 210mAh/g, and the first-cycle efficiency is 76.5%; the capacity was 168mAh/g and the capacity retention was 92% after 150 cycles at a current density of 100mA/g (FIG. 6).
Example 2
According to Li1.15Ni0.28Mn0.57O2Adding lithium carbonate, nickel oxide and manganese carbonate in stoichiometric ratio into a ball milling tank, adding a certain amount of mixed solvent of water and acetone in a mass ratio of 1:1 according to 30% of solid content, ball milling for 6 hours, and then adding boronAcid and ammonium dihydrogen phosphate, wherein the molar weight of boron element accounts for Li1.15Ni0.28Mn0.57O21% of the molar amount of the phosphorus element in the Li1.15Ni0.28Mn0.57O2And (3) continuously performing ball milling for 1h according to the molar weight of 0.5%. And then drying the obtained slurry by a spray dryer, calcining the obtained powder in a muffle furnace at 450 ℃ for 5h, then heating to 900 ℃ for calcining for 12h, cooling, crushing and sieving to obtain the target product. The tap density is 2.26g/cm3。
Example 3
According to Li1.2Ni0.2Mn0.6O2The chemical formula is that lithium hydroxide, nickel carbonate and manganese sesquioxide with stoichiometric ratio are added into a ball milling tank, a certain amount of ethanol is added as a solvent according to 40 percent of solid content, ball milling is carried out for 6 hours, then borax and ammonium dihydrogen phosphate are added, wherein the molar weight of boron element accounts for Li1.2Ni0.2Mn0.6O21.5% of the molar amount of the phosphorus element in the Li1.2Ni0.2Mn0.6O2And (3) continuously performing ball milling for 1h according to the molar weight of 0.5%. And then drying the obtained slurry by a spray dryer, calcining the obtained powder in a muffle furnace at 450 ℃ for 5h, then heating to 900 ℃ for calcining for 12h, cooling, crushing and sieving to obtain the target product. The tap density is 2.25g/cm3。
Example 4
According to Li1.2Ni0.13Co0.13Mn0.54O2The chemical formula is that lithium carbonate, nickel oxide, manganese oxide and cobalt carbonate with stoichiometric ratio are added into a ball milling tank, a certain amount of N-methyl pyrrolidone is added as a solvent according to 25 percent of solid content, and ball milling is carried out for 6 hours. Then adding diboron trioxide and ammonium dihydrogen phosphate, wherein the molar weight of boron element accounts for Li1.2Ni0.13Co0.13Mn0.54O21.5% of the molar amount of the phosphorus element in the Li1.2Ni0.13Co0.13Mn0.54O2And (4) continuing ball milling for 1h according to the molar weight of 1%. Drying the obtained slurry with a spray dryer to obtain powder at 450 deg.C in a muffle furnaceCalcining for 5h, then heating to 900 ℃, calcining for 12h, cooling, crushing and sieving to obtain the target product. The tap density is 2.27g/cm3。
Example 5
According to Li1.2Ni0.13Co0.13Mn0.54O2Adding lithium carbonate, nickel oxide, manganese oxide and cobalt carbonate in stoichiometric ratio into a ball milling tank, adding a certain amount of water as a solvent according to the solid content of 25%, and carrying out ball milling for 6 hours. Then adding diboron trioxide and ammonium dihydrogen phosphate, wherein the molar weight of the added boron element accounts for Li1.2Ni0.13Co0.13Mn0.54O20.1% of the molar amount of the added phosphorus element in the amount of Li1.2Ni0.13Co0.13Mn0.54O2And (3) continuing ball milling for 1h according to 0.1 percent of the molar weight. And then drying the obtained slurry by a spray dryer, calcining the obtained powder in a muffle furnace at 450 ℃ for 5h, heating to 900 ℃ for 12h, cooling, crushing and sieving to obtain the target product. The tap density is 2.15g/cm3。
Example 6
According to the chemical formula, lithium carbonate, nickel oxide, manganese oxide and cobalt carbonate in stoichiometric ratio are added into a ball milling tank, a certain amount of water is added according to the solid content of 25%, the ball milling is carried out for 6 hours, then diboron trioxide and ammonium dihydrogen phosphate are added, wherein the molar weight of the added boron element accounts for Li1.2Ni0.13Co0.13Mn0.54O25% of the mol weight, the mol weight of the added phosphorus element accounts for Li1.2Ni0.13Co0.13Mn0.54O2And 5 percent of the molar weight, and continuing the ball milling for 1 hour. And then drying the obtained slurry by a spray dryer, calcining the obtained powder in a muffle furnace at 450 ℃ for 5h, heating to 900 ℃ for 12h, cooling, crushing and sieving to obtain the target product. The tap density is 2.37g/cm3。
Comparative example 1
According to Li1.15Ni0.28Mn0.57O2The chemical formula is that lithium carbonate, nickel nitrate and manganese dioxide in stoichiometric ratio are addedAnd putting the mixture into a ball milling tank, adding a certain amount of mixed solvent of ethanol and water in a mass ratio of 1:1 according to 40% of solid content, and carrying out ball milling for 6 hours. And then drying the obtained slurry by a spray dryer, calcining the obtained powder in a muffle furnace at 450 ℃ for 5h, heating to 900 ℃ for 12h, cooling, crushing and sieving to obtain the target product. The button cell is assembled by the material and the electrochemical performance is tested.
The SEM image of the target product is shown in FIG. 2, and it can be seen that the material has a loose particle structure and many pores are formed among the primary particles. The tap density was found to be 1.12g/cm3. The electrochemical test results are shown in FIG. 5, the first cycle specific discharge capacity is 197mAh/g, and the first cycle efficiency is 72.3%.
Comparative example 2
According to Li1.2Ni0.13Co0.13Mn0.54O2Adding lithium carbonate, nickel oxide and manganese oxide in stoichiometric ratio into a ball milling tank, adding a certain amount of N-methylpyrrolidone as a solvent according to the solid content of 15%, and carrying out ball milling for 6 hours. And then drying the obtained slurry by a spray dryer, calcining the obtained powder in a muffle furnace at 450 ℃ for 5h, heating to 900 ℃ for 12h, cooling, crushing and sieving to obtain the target product.
Comparative example 3
According to Li1.15Ni0.28Mn0.57O2Adding lithium carbonate, nickel nitrate and manganese dioxide in stoichiometric ratio into a ball milling tank, adding a certain amount of mixed solvent of ethanol and water in a mass ratio of 1:1 according to 40% of solid content, carrying out ball milling for 6 hours, adding 2% of diboron trioxide, and continuing to carry out ball milling for 1 hour. And then drying the slurry by a spray dryer, calcining the obtained powder in a muffle furnace at 450 ℃ for 5h, heating to 900 ℃ for 12h, cooling, crushing and sieving to obtain the target product.
Comparative example 4
According to Li1.15Ni0.28Mn0.57O2Adding lithium carbonate, nickel nitrate and manganese dioxide in stoichiometric ratio into a ball milling tank, adding a certain amount of mixed solvent of ethanol and water in a mass ratio of 1:1 according to 40% of solid content, and ball milling for 6 hoursThen 2% of phosphorus pentoxide is added, and the ball milling is continued for 1 h. And then drying the slurry by a spray dryer, calcining the obtained powder in a muffle furnace at 450 ℃ for 5h, heating to 900 ℃ for 12h, cooling, crushing and sieving to obtain the target product.
The samples obtained in examples and comparative examples were tested for tap density and electrochemical properties under the same conditions, and the test results are shown in table 1 below.
TABLE 1 tap Density and electrochemical Performance test results
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A preparation method of a lithium-rich manganese-based positive electrode material of a high tap density lithium ion battery is characterized by comprising the following steps:
a. mixing a lithium source, a nickel source, a cobalt source and a manganese source compound according to a stoichiometric ratio, adding a solvent, and uniformly grinding by using a ball milling or sanding mode to obtain uniform slurry;
b. adding a boron source compound and a phosphorus source compound into the obtained slurry, continuously grinding, and uniformly mixing;
c. drying the slurry obtained in the step b by using a spray dryer to obtain spherical precursor powder;
d. calcining the obtained precursor powder at high temperature: presintering at 400-500 ℃ for 1-6h, then heating to 800-1000 ℃ for calcining for 8-24h, cooling and crushing to obtain the target product.
2. The method according to claim 1, wherein in the step a, the lithium source compound is selected from any one or more of lithium oxide, lithium carbonate, lithium nitrate, lithium hydroxide, lithium acetate, and lithium oxalate; the nickel source compound is selected from any one or more of nickel oxide, nickel carbonate, basic nickel carbonate, nickel nitrate, nickel acetate and nickel oxalate; the manganese source compound is selected from any one or more of manganese dioxide, manganese sesquioxide, manganese monoxide, manganese carbonate, manganese nitrate, manganese acetate and manganese oxalate; the cobalt source compound is selected from any one or more of cobaltosic oxide, cobalt carbonate, cobalt nitrate, cobalt acetate and cobalt oxalate.
3. The method according to claim 1, wherein the lithium-rich manganese-based positive electrode material has a chemical formula of: li [ Li ]xNiaCobMnc]O2，a+b+c+x＝1，0<a<1、0≤b<1，0<c<1，0<x≤0.33。
4. The method according to claim 1, wherein in step a, the solvent is any one or a mixture of ethanol, water, acetone and N-methylpyrrolidone.
5. The process of claim 1, wherein in step a, the solvent is added in an amount of 10 to 50% solids.
6. The method according to claim 1, wherein in the step b, the boron source compound is selected from any one or more of diboron trioxide, borax, boric acid and lithium borate; the phosphorus source compound is selected from one or more of phosphorus pentoxide, ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate and potassium phosphate.
7. The method according to claim 1, wherein in the step b, the boron element is added in a molar amount based on the target product Li [ Li ]xNiaCobMnc]O20.1-5% of molar weight, and the molar weight of the added phosphorus element accounts for the target product Li [ ]xNiaCobMnc]O20.1-5% of the molar weight.
8. A lithium-rich manganese-based positive electrode material of a high tap density lithium ion battery is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The lithium-rich manganese-based positive electrode material of claim 8, wherein the tap density of the positive electrode material is 2.1g/cm3The above.
10. A lithium ion battery is characterized in that the positive electrode material of the lithium ion battery is the lithium-rich manganese-based positive electrode material with the high tap density as defined in any one of claims 8 to 9, or the lithium-rich manganese-based positive electrode material with the high tap density as prepared by the preparation method as defined in any one of claims 1 to 7.
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| CN102148367A (en) * | 2010-02-08 | 2011-08-10 | 江西省金锂科技有限公司 | Method for preparing lithium-ion battery anode material of lithium iron phosphate |
| JP2014241229A (en) * | 2013-06-11 | 2014-12-25 | 電気化学工業株式会社 | Conductive composite particle, secondary battery positive electrode arranged by use thereof, and secondary battery |
| CN108598457A (en) * | 2018-04-23 | 2018-09-28 | 桑德集团有限公司 | A kind of monocrystalline lithium-rich manganese-based anode material and preparation method thereof, lithium ion battery |
| CN109216688A (en) * | 2018-10-23 | 2019-01-15 | 桑顿新能源科技有限公司 | A kind of ternary lithium electric material, preparation method and lithium ion battery |
| CN110391417A (en) * | 2019-07-16 | 2019-10-29 | 湖南长远锂科股份有限公司 | The preparation method of one type monocrystalline lithium-rich manganese-based anode material |
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| WO2023130784A1 (en) * | 2022-01-10 | 2023-07-13 | 华北理工大学 | Additive for reducing roasting temperature of fluxed magnetite pellets and use method |
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