CN116247184A - Nano lithium nickelate coated modified lithium manganate positive electrode material and preparation method and application thereof - Google Patents

Nano lithium nickelate coated modified lithium manganate positive electrode material and preparation method and application thereof Download PDF

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CN116247184A
CN116247184A CN202310161317.2A CN202310161317A CN116247184A CN 116247184 A CN116247184 A CN 116247184A CN 202310161317 A CN202310161317 A CN 202310161317A CN 116247184 A CN116247184 A CN 116247184A
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lithium
lithium manganate
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CN116247184B (en
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马岩华
贺兆书
陈鹏鹛
陈静波
王剑锋
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Anhui Boshi Hi Hi Tech New Material Co ltd
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a nano lithium nickelate coated modified lithium manganate positive electrode material, which comprises a lithium manganate matrix formed by aggregation of primary particles and a nano lithium nickelate layer coated on the surface of the lithium manganate matrix, wherein the nano lithium nickelate layer is continuously coated on the surface of the lithium manganate matrix, and the nano lithium nickelate is filled in pores among the primary particles on the surface of the lithium manganate matrix in a wedge-shaped form. In the invention, nano lithium nickelate is filled and coated in the pores of primary particles on the surface layer of a lithium manganate matrix and takes a wedge shape; on the surface of the secondary particles, nano lithium nickelate is covered and coated and is in a film form. The nano lithium nickelate coated modified lithium manganate anode material provided by the invention has a very small specific surface area, can effectively isolate direct contact between lithium manganate and electrolyte, reduces dissolution of manganese ions, can improve the first coulomb efficiency and specific discharge capacity of lithium manganate, and also improves the cycle performance, particularly the high-temperature cycle performance and the high-temperature storage performance of lithium manganate.

Description

Nano lithium nickelate coated modified lithium manganate positive electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a nano lithium nickelate coated modified lithium manganate positive electrode material, a preparation method and application thereof.
Background
Along with the rapid development of new energy technology, the lithium ion battery is gradually applied to the fields of digital products, new energy automobiles, energy storage power stations and the like by virtue of the advantages of high energy density, no memory effect, long service life, environmental friendliness and the like. The lithium manganate has the advantages of simple preparation process, lower raw material cost, good safety performance and the like, and becomes a commercialized lithium ion battery anode material.
However, lithium manganate also has the following problems: (1) The ginger-taylor effect easily occurs during circulation, leading to Mn 2+ Dissolving ions; (2) The electrolyte is directly contacted with the material to cause corrosion of disposable particles on the surface of the material; (3) Electrolyte enters the interior from the pores on the surface of the material, so that disposable particles in the material are corroded; these problems make the cycling performance of lithium manganate poor. The specific capacity of the current commercial lithium manganate is low and is generally 100-115 mAh/g, so that the requirement of a high-energy-density battery is difficult to meet. In the prior art, the modification method of lithium manganate mainly comprises the following steps: the doped metal ions can stabilize the crystal structure of the lithium manganate material; the surface coating method can avoid direct contact between the material and the electrolyte, and reduce corrosion of the electrolyte to the material; the specific surface area of the material can be reduced by controlling the morphology of lithium manganate, so that the interface area of manganese dissolution is reduced.
Chinese patent publication No. CN104409719B disclosesA porous spherical lithium manganate positive electrode material and a preparation method thereof are provided, wherein the porous spherical lithium manganate material is formed by stacking nano-scale particles with the diameter of 500 nm-2 um, and the average pore diameter of 10-100 nm. The preparation method comprises dissolving manganese salt in water solution, and adding a certain amount of hydrogen peroxide; adding an aqueous solution of sodium carbonate and sodium hydroxide into the aqueous solution to obtain a precipitate; and mixing the precipitate with lithium carbonate, and roasting at 700 ℃ for 3-10 hours to obtain the porous lithium manganate material. The porous spherical lithium manganate positive electrode material obtained by the method has large specific surface area and excellent electrochemical performance, and the preferable specific surface area is 5-34 m 2 And/g. However, the increase of the specific surface area leads to the increase of the contact area between the electrolyte and the diameter of the material, which increases the degree of side reaction at the interface of the material and aggravates the dissolution of manganese ions, resulting in poor cycle performance of the material.
Chinese patent publication No. CN111193007a discloses a positive electrode of lithium manganate material battery, its preparation method and lithium manganate battery, the positive electrode includes lithium manganate main body and tin oxide coating layer coated outside the lithium manganate main body. The lithium manganate battery adopts the tin oxide coated lithium manganate positive electrode material, has higher specific capacity and good cycle performance, and has better high-temperature cycle performance. The outer layer of tin oxide keeps the protection of the inner lithium manganate for a longer time, prevents the corrosion of the outer HF on the lithium manganate, and further effectively improves the cycle stability of the material. However, tin oxide cannot provide more lithium ions to participate in the charge and discharge process of the material, and the tin oxide also occupies a certain mass percentage in the material, so that the first coulomb efficiency of the lithium manganate material is reduced, the specific capacity of the material is reduced, the dosage of the negative electrode is increased, and the energy density of the battery is reduced.
Chinese patent publication No. CN103606664a discloses a method for preparing lithium manganate coated lithium manganate positive electrode material. Preparing lithium salt, nickel salt and manganese salt into a solution, adding lithium manganate into the solution, stirring for 20-120 minutes, and drying at 80-120 ℃ for 6-24 hours to obtain a dried sample; heating the dried sample to 400-700 ℃ at a speed of 2-10 ℃/min in air atmosphere and keeping the temperature for 1-10 hours, and then naturally cooling to obtain a pre-baked sample; grinding and crushing the pre-baked sample, heating to 600-950 ℃ at the speed of 2-10 ℃/min, keeping the temperature for 3-20 hours, reducing to 300-600 ℃ at the speed of 2-10 ℃/min, and naturally cooling to obtain the lithium nickel manganese oxide coated lithium manganate anode material. The lithium manganate material prepared by the method has better high-temperature cycle performance, but the charging platform of the lithium nickel manganate is far higher than the upper limit cut-off voltage of a lithium manganate battery by 4.8V, so that the lithium nickel manganate has no capacity in the charging and discharging voltage interval (3.0-4.3V) of the lithium manganate, the specific capacity of the lithium manganate material can be reduced, and the specific capacity of the modified lithium manganate is less than 105mAh/g. Moreover, when lithium manganate is added into a solution prepared from lithium salt, nickel salt and manganese salt, the solution can enter the internal pores of the material due to capillary effect generated by the surface tension of the aqueous solution, and a lithium nickel manganate precursor is generated in the lithium manganate in the next coprecipitation reaction process, so that the coating effect of the lithium nickel manganate is deteriorated.
The existing solid-phase coating method mostly adopts nano inorganic oxide as a coating agent, the thickness of the coating is directly related to the particle size of the nano oxide, the discontinuous coating and the too thick coating are caused by the characteristic that the inorganic oxide is difficult to disperse, and the nano inorganic oxide generally has no electrochemical activity, so that the specific discharge capacity of the material is reduced, and the electrochemical performance of the material is influenced. In the conventional liquid phase coating method, an aqueous solution containing metal salt is often used as a coating agent, and water also dissolves lithium ions on the surface of lithium manganate, so that the material performance is deteriorated. Meanwhile, under the action of capillary phenomenon, the solution can infiltrate into the material through pores on the surface of the material, so that inorganic oxide is deposited and crystallized and grows up in the material particles, the internal stress of the material is increased, and the cycle performance of the material is deteriorated. Therefore, the current lithium manganate anode material has low coulombic efficiency, low specific discharge capacity and poor cycle performance, especially poor high-temperature cycle performance and high-temperature storage performance for the first time.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a nano lithium nickelate coated modified lithium manganate positive electrode material, a preparation method and application thereof.
The invention provides a nano lithium nickelate coated modified lithium manganate positive electrode material, which comprises a lithium manganate matrix formed by aggregation of primary particles and a nano lithium nickelate layer coated on the surface of the lithium manganate matrix, wherein the nano lithium nickelate layer is continuously coated on the surface of the lithium manganate matrix, and the nano lithium nickelate is filled in pores among the primary particles on the surface of the lithium manganate matrix in a wedge-shaped form.
Preferably, the thickness of the nano lithium nickelate layer is 10-800 nm, and the nano lithium nickelate layer is coated on the surface of the lithium manganate matrix continuously in a non-uniform thickness.
Preferably, the specific surface area of the positive electrode material is 0.1-0.5 m 2 /g。
The invention also provides a preparation method of the nano lithium nickelate coated modified lithium manganate anode material, which comprises the following steps:
a) Adding a lithium manganate matrix into a mixed solution of a surfactant and a dispersing agent, and mixing to obtain a surfactant-coated lithium manganate matrix I, wherein the surfactant is selected from water-insoluble or slightly water-soluble organic carboxylic acid;
b) Adding the lithium manganate matrix I wrapped by the surfactant into a nickel salt aqueous solution, mixing, and aging to obtain a lithium manganate matrix II;
c) And mixing the lithium source compound with a lithium manganate matrix II, and sintering to obtain the nano lithium nickelate coated modified lithium manganate anode material.
Preferably, the surfactant is selected from one or more of benzoic acid, phthalic acid, caproic acid, heptanoic acid, caprylic acid, isooctanoic acid, pelargonic acid, capric acid, palmitic acid, oleic acid, stearic acid.
Preferably, the dispersing agent is selected from one or more of ethanol, diethyl ether, acetone, chloroform and pyridine;
the mass ratio of the surfactant to the dispersant is 0.01-5: 1.
preferably, the nickel salt is selected from one or more of nickel nitrate, nickel sulfate, nickel chloride, nickel acetate;
the molar concentration of the nickel salt aqueous solution is 1-6 mol/L.
Preferably, the lithium source compound is selected from one or more of lithium carbonate, lithium hydroxide, lithium nitrate;
the mass ratio of the lithium source compound to the lithium manganate matrix II is 0.005-0.1: 1.
preferably, the aging time is 0.5-12 hours;
the sintering temperature is 600-850 ℃, and the sintering time is 2-12 h.
The invention also provides a lithium ion battery, which comprises the nano lithium nickelate coated modified lithium manganate anode material or the nano lithium nickelate coated modified lithium manganate anode material prepared by the preparation method.
Compared with the prior art, the invention provides a nano lithium nickelate coated modified lithium manganate positive electrode material, which comprises a lithium manganate matrix formed by aggregation of primary particles and a nano lithium nickelate layer coated on the surface of the lithium manganate matrix, wherein the nano lithium nickelate layer is continuously coated on the surface of the lithium manganate matrix, and the nano lithium nickelate is filled in pores among the primary particles on the surface layer of the lithium manganate matrix in a wedge-shaped form. In the positive electrode material provided by the invention, nano lithium nickelate is filled and coated in pores of primary particles on the surface layer of a lithium manganate matrix and takes a wedge shape; on the surface of the secondary particles, nano lithium nickelate is covered and coated and is in a film form. The nano lithium nickelate coated modified lithium manganate anode material provided by the invention has a very small specific surface area, can effectively isolate direct contact between lithium manganate and electrolyte, reduces dissolution of manganese ions, can improve the first coulomb efficiency and specific discharge capacity of lithium manganate, and also improves the cycle performance, particularly the high-temperature cycle performance and the high-temperature storage performance of lithium manganate.
The invention also provides a preparation method of the nano lithium nickelate coated modified lithium manganate anode material, which comprises the following steps: a) Adding a lithium manganate matrix into a mixed solution of a surfactant and a dispersing agent, and mixing to obtain a surfactant-coated lithium manganate matrix I, wherein the surfactant is selected from water-insoluble or slightly water-soluble organic carboxylic acid; b) Adding the lithium manganate matrix I wrapped by the surfactant into a nickel salt aqueous solution, mixing, and aging to obtain a lithium manganate matrix II; c) And mixing the lithium source compound with a lithium manganate matrix II, and sintering to obtain the nano lithium nickelate coated modified lithium manganate anode material. The invention uses the properties of high density and small capillary phenomenon of the organic carboxylic acid to ensure that the organic carboxylic acid can not infiltrate into the material from the pores on the surface of the material, and can only construct a layer of non-uniform thickness continuous organic liquid film on the lithium manganate matrix. The organic carboxylic acid is more retained at the pores of the primary particles and less retained at the surface of the primary particles. The lithium manganate material coated by organic nickel is obtained through ion exchange reaction with nickel salt solution. Because the surface of the organic carboxylic acid is hydrophobic, the organic nickel can maintain a continuous liquid film form with a non-uniform thickness in the solution. Then, the organic nickel coating layer and the lithium source react at high temperature to obtain the nano lithium nickelate coating layer with controllable size. At the pores of the primary particles, the nano lithium nickelate is filled and coated and takes a wedge shape; on the surface of the secondary particles, nano lithium nickelate is covered and coated and is in a film form. The modified lithium manganate material obtained by the invention has very small specific surface area, can effectively isolate direct contact of lithium manganate and electrolyte, reduces elution of manganese ions, can improve the first coulomb efficiency and specific discharge capacity of lithium manganate, and also improves the cycle performance, particularly the high-temperature cycle performance and the high-temperature storage performance of lithium manganate. The preparation method is simple, the production process is controllable, and the preparation method is suitable for large-scale industrial application.
Drawings
FIG. 1 is a schematic structural diagram of a nano lithium nickelate coated modified lithium manganate material according to the invention;
FIG. 2 is a scanning electron microscope image of the nano lithium nickelate coated modified lithium manganate material prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a lithium manganate material of comparative example 1 of the present invention;
fig. 4 is a graph showing the first charge-discharge curves of the batteries fabricated in example 1, comparative example 1 and comparative example 2;
fig. 5 is a graph showing the cycle performance curves of the batteries fabricated in example 1, comparative example 1 and comparative example 2;
fig. 6 is a graph showing the high-temperature cycle performance curves of the batteries fabricated in example 1, comparative example 1 and comparative example 2.
Detailed Description
The invention provides a nano lithium nickelate coated modified lithium manganate positive electrode material, which comprises a lithium manganate matrix formed by aggregation of primary particles and a nano lithium nickelate layer coated on the surface of the lithium manganate matrix, wherein the nano lithium nickelate layer is continuously coated on the surface of the lithium manganate matrix, and the nano lithium nickelate is filled in pores among the primary particles on the surface of the lithium manganate matrix in a wedge-shaped form.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a nano lithium nickelate coated modified lithium manganate material according to the present invention.
In the present invention, the thickness of the nano lithium nickel oxide layer is 10 to 800nm, preferably 20 to 500nm, and more preferably 20 to 200nm.
The specific surface area of the nano lithium nickelate coated modified lithium manganate positive electrode material is 0.1-0.5 m 2 Preferably 0.1, 0.2, 0.3, 0.4, 0.5, or 0.1 to 0.5m 2 Any value between/g.
The nano lithium nickelate coated modified lithium manganate anode material has a smooth surface and no obvious pore structure.
The invention also provides a preparation method of the nano lithium nickelate coated modified lithium manganate anode material, which comprises the following steps:
a) Adding a lithium manganate matrix into a mixed solution of a surfactant and a dispersing agent, and mixing to obtain a surfactant-coated lithium manganate matrix I, wherein the surfactant is selected from water-insoluble or slightly water-soluble organic carboxylic acid;
b) Adding the lithium manganate matrix I wrapped by the surfactant into a nickel salt aqueous solution, mixing, and aging to obtain a lithium manganate matrix II;
c) And mixing the lithium source compound with a lithium manganate matrix II, and sintering to obtain the nano lithium nickelate coated modified lithium manganate anode material.
The invention firstly prepares a mixed solution of a surfactant and a dispersing agent, wherein the surfactant is selected from organic carboxylic acid which is insoluble or slightly soluble in water, preferably one or more of benzoic acid, phthalic acid, caproic acid, heptanoic acid, caprylic acid, isooctanoic acid, nonanoic acid, capric acid, palmitic acid, oleic acid and stearic acid, and further preferably one or more of benzoic acid, phthalic acid, caprylic acid, isooctanoic acid, palmitic acid, oleic acid and stearic acid; more preferably one or more of benzoic acid, phthalic acid, octanoic acid, isooctanoic acid.
The dispersing agent is selected from one or more of ethanol, diethyl ether, acetone, chloroform and pyridine, more preferably one or more of ethanol, diethyl ether and acetone, and still more preferably one or more of ethanol and diethyl ether.
The mass ratio of the surfactant to the dispersant is 0.01-5: 1, preferably 0.2 to 2:1, more preferably 0.5 to 1:1.
and adding the lithium manganate matrix into the mixed solution of the surfactant and the dispersing agent, mixing, taking out the lithium manganate matrix after fully stirring, and washing, filtering and standing to obtain the surfactant-coated lithium manganate matrix I.
The source of the lithium manganate matrix is not particularly limited, and the lithium manganate matrix can be commercially available lithium manganate or lithium manganate prepared by self according to a method in the prior art.
The time for the standing is 0.1 to 4 hours, preferably 0.5 to 2 hours.
Then adding the lithium manganate matrix I wrapped by the surfactant into nickel salt aqueous solution, mixing and stirring, aging, washing, filtering and drying a product to obtain a lithium manganate matrix II;
wherein the nickel salt is selected from one or more of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate, and preferably one or more of nickel nitrate and nickel acetate.
The molar concentration of the aqueous nickel salt solution is 1 to 6mol/L, preferably 1, 2, 3, 4, 5, 6, or any value between 1 and 6mol/L.
The aging time is 0.5 to 12 hours, preferably 1 to 5 hours.
And after the lithium manganate matrix II is obtained, mixing the lithium source compound with the lithium manganate matrix II, and sintering to obtain the nano lithium nickelate coated modified lithium manganate anode material.
Wherein the lithium source compound is selected from lithium carbonate;
the mass ratio of the lithium source compound to the lithium manganate matrix II is 0.005-0.1: 1, preferably 0.01 to 0.05:1.
the sintering temperature is 600-850 ℃, preferably 650-750 ℃, and the sintering time is 2-12 h, preferably 3-6 h.
The invention also provides a lithium ion battery, which comprises the nano lithium nickelate coated modified lithium manganate anode material or the nano lithium nickelate coated modified lithium manganate anode material prepared by the preparation method.
In the positive electrode material provided by the invention, nano lithium nickelate is filled and coated in pores of primary particles on the surface layer of a lithium manganate matrix and takes a wedge shape; on the surface of the secondary particles, nano lithium nickelate is covered and coated and is in a film form. The nano lithium nickelate coated modified lithium manganate anode material provided by the invention has a very small specific surface area, can effectively isolate direct contact between lithium manganate and electrolyte, reduces dissolution of manganese ions, can improve the first coulomb efficiency and specific discharge capacity of lithium manganate, and also improves the cycle performance, particularly the high-temperature cycle performance and the high-temperature storage performance of lithium manganate.
The invention uses the properties of high density and small capillary phenomenon of the organic carboxylic acid to ensure that the organic carboxylic acid can not infiltrate into the material from the pores on the surface of the material, and can only construct a layer of non-uniform thickness continuous organic liquid film on the lithium manganate matrix. The organic carboxylic acid is more retained at the pores of the surface layer primary particles, less retained at the surface of the surface layer primary particles, and not retained inside the secondary particles. The lithium manganate material coated by organic nickel is obtained through ion exchange reaction with nickel salt solution. Because the surface of the organic carboxylic acid is hydrophobic, the organic nickel can maintain a continuous liquid film form with a non-uniform thickness in the solution. Then, the organic nickel coating layer and the lithium source react at high temperature to obtain the nano lithium nickelate coating layer with controllable size. At the pores of the primary particles, the nano lithium nickelate is filled and coated and takes a wedge shape; on the surface of the secondary particles, nano lithium nickelate is covered and coated and is in a film form. The nano lithium nickel oxide does not enter the pores inside the secondary particles. If nano lithium nickelate is deposited in the lithium manganate secondary particles, because the expansion coefficients of lithium nickelate and lithium manganate for lithium ion intercalation and deintercalation are different, larger stress can be generated in the lithium manganate secondary particles, so that the lithium manganate material is broken in the charge-discharge cycle process, and the cycle performance is deteriorated. The modified lithium manganate material obtained by the invention has very small specific surface area, can effectively isolate direct contact of lithium manganate and electrolyte, reduces elution of manganese ions, can improve the first coulomb efficiency and specific discharge capacity of lithium manganate, and also improves the cycle performance, particularly the high-temperature cycle performance and the high-temperature storage performance of lithium manganate. The preparation method is simple, the production process is controllable, and the preparation method is suitable for large-scale industrial application.
In order to further understand the present invention, the following examples are provided to illustrate the modified lithium manganate anode material coated with nano lithium nickelate, the preparation method and the application thereof, and the protection scope of the present invention is not limited by the following examples.
Example 1
S1: preparing isooctanoic acid and ethanol according to the mass ratio of 0.5:1, preparing a nickel nitrate aqueous solution with the molar concentration of 4 mol/L;
s2: adding the lithium manganate matrix into the mixed solution, fully stirring, taking out the lithium manganate matrix, washing, filtering, and standing for 0.5h to obtain a lithium manganate matrix I wrapped by isooctanoic acid;
s3: adding the lithium manganate matrix I into a prepared nickel nitrate aqueous solution, slowly stirring, aging for 1h, and washing, filtering and drying to obtain a lithium manganate matrix II;
s4: mixing lithium carbonate with a lithium manganate matrix II according to a mass ratio of 0.01:1, and sintering for 4 hours at 650 ℃ to obtain the nano lithium nickelate coated modified lithium manganate anode material. The thickness of the nano lithium nickelate layer is 30-200 nm, and the nano lithium nickelate layer is coated on the surface of the lithium manganate matrix continuously in a non-uniform thickness.
Example 2
S1: preparing benzoic acid and ethanol according to a mass ratio of 2:1, preparing a nickel sulfate aqueous solution with a molar concentration of 5 mol/L;
s2: adding the lithium manganate matrix into the mixed solution, fully stirring, taking out the lithium manganate matrix, washing, filtering and standing for 1h to obtain a benzoic acid-coated lithium manganate matrix I;
s3: adding the lithium manganate matrix I into the prepared nickel sulfate aqueous solution, slowly stirring, aging for 2 hours, and washing, filtering and drying to obtain a lithium manganate matrix II;
s4: mixing lithium carbonate with a lithium manganate matrix II according to a mass ratio of 0.005:1, and sintering for 5 hours at 600 ℃ to obtain the nano lithium nickelate coated modified lithium manganate anode material. The thickness of the nano lithium nickelate layer is 10-100 nm, and the nano lithium nickelate layer is coated on the surface of the lithium manganate matrix continuously in a non-uniform thickness.
Example 3
S1: preparing decanoic acid and diethyl ether according to the mass ratio of 1.8:1, preparing a nickel chloride aqueous solution with the molar concentration of 6 mol/L;
s2: adding the lithium manganate matrix into the mixed solution, fully stirring, taking out the lithium manganate matrix, washing, filtering, and standing for 2 hours to obtain a lithium manganate matrix I wrapped by decanoic acid;
s3: adding the lithium manganate matrix I into the prepared nickel chloride aqueous solution, slowly stirring, aging for 2 hours, and washing, filtering and drying to obtain a lithium manganate matrix II;
s4: mixing lithium carbonate with a lithium manganate matrix II according to a mass ratio of 0.02:1, and sintering for 10 hours at 700 ℃ to obtain the nano lithium nickelate coated modified lithium manganate anode material. The thickness of the nano lithium nickelate layer is 50-400 nm, and the nano lithium nickelate layer is coated on the surface of the lithium manganate matrix continuously in a non-uniform thickness.
Example 4
S1: preparing octanoic acid and acetone according to a mass ratio of 4:1, preparing a nickel acetate aqueous solution with the molar concentration of 2 mol/L;
s2: adding the lithium manganate matrix into the mixed solution, fully stirring, taking out the lithium manganate matrix, washing, filtering and standing for 3 hours to obtain a lithium manganate matrix I wrapped by octanoic acid;
s3: adding the lithium manganate matrix I into the prepared nickel acetate aqueous solution, slowly stirring, aging for 10 hours, and washing, filtering and drying to obtain a lithium manganate matrix II;
s4: mixing lithium carbonate with a lithium manganate matrix II according to a mass ratio of 0.06:1, and sintering for 8 hours at 650 ℃ to obtain the nano lithium nickelate coated modified lithium manganate anode material. The thickness of the nano lithium nickelate layer is 100-800 nm, and the nano lithium nickelate layer is coated on the surface of the lithium manganate matrix continuously in a non-uniform thickness.
Example 5
S1: preparing palmitic acid and ethanol according to a mass ratio of 1:1, preparing a nickel nitrate aqueous solution with a molar concentration of 5 mol/L;
s2: adding the lithium manganate matrix into the mixed solution, fully stirring, taking out the lithium manganate matrix, washing, filtering and standing for 1h to obtain a lithium manganate matrix I wrapped by palmitic acid;
s3: adding the lithium manganate matrix I into a prepared nickel nitrate aqueous solution, slowly stirring, aging for 5 hours, and washing, filtering and drying to obtain a lithium manganate matrix II;
s4: mixing lithium carbonate with a lithium manganate matrix II according to a mass ratio of 0.01:1, and sintering at 680 ℃ for 9 hours to obtain the nano lithium nickelate coated modified lithium manganate anode material. The thickness of the nano lithium nickelate layer is 25-200 nm, and the nano lithium nickelate layer is coated on the surface of the lithium manganate matrix continuously in a non-uniform thickness.
Example 6
S1: preparing isooctanoic acid and pyridine according to a mass ratio of 2.5:1, preparing a nickel nitrate aqueous solution with the molar concentration of 2 mol/L;
s2: adding the lithium manganate matrix into the mixed solution, fully stirring, taking out the lithium manganate matrix, washing, filtering, and standing for 1.5 hours to obtain a lithium manganate matrix I wrapped by isooctanoic acid;
s3: adding the lithium manganate matrix I into the prepared nickel nitrate aqueous solution, slowly stirring, aging for 1.5 hours, and washing, filtering and drying to obtain a lithium manganate matrix II;
s4: mixing lithium carbonate with a lithium manganate matrix II according to a mass ratio of 0.01:1, and sintering for 2 hours at 850 ℃ to obtain the nano lithium nickelate coated modified lithium manganate anode material. The thickness of the nano lithium nickelate layer is 20-150 nm, and the nano lithium nickelate layer is coated on the surface of the lithium manganate matrix continuously in a non-uniform thickness.
Example 7
S1: preparing phthalic acid and ethanol according to the mass ratio of 1.5:1, preparing a nickel sulfate aqueous solution with the molar concentration of 2 mol/L;
s2: adding the lithium manganate matrix into the mixed solution, fully stirring, taking out the lithium manganate matrix, washing, filtering and standing for 1h to obtain a phthalic acid coated lithium manganate matrix I;
s3: adding the lithium manganate matrix I into the prepared nickel sulfate aqueous solution, slowly stirring, aging for 2.5 hours, and washing, filtering and drying to obtain a lithium manganate matrix II;
s4: mixing lithium carbonate with a lithium manganate matrix II according to a mass ratio of 0.03:1, and sintering for 4 hours at 810 ℃ to obtain the nano lithium nickelate coated modified lithium manganate anode material. The thickness of the nano lithium nickelate layer is 50-400 nm, and the nano lithium nickelate layer is coated on the surface of the lithium manganate matrix continuously in a non-uniform thickness.
Example 8
S1: preparing isooctanoic acid and ethanol according to the mass ratio of 0.2:1, preparing a nickel nitrate aqueous solution with a molar concentration of 5 mol/L;
s2: adding the lithium manganate matrix into the mixed solution, fully stirring, taking out the lithium manganate matrix, washing, filtering, and standing for 0.15h to obtain a lithium manganate matrix I wrapped by isooctanoic acid;
s3: adding the lithium manganate matrix I into a prepared nickel nitrate aqueous solution, slowly stirring, aging for 7 hours, and washing, filtering and drying to obtain a lithium manganate matrix II;
s4: mixing lithium carbonate with a lithium manganate matrix II according to a mass ratio of 0.02:1, and sintering for 6 hours at 730 ℃ to obtain the nano lithium nickelate coated modified lithium manganate anode material. The thickness of the nano lithium nickelate layer is 30-400 nm, and the nano lithium nickelate layer is coated on the surface of the lithium manganate matrix continuously in a non-uniform thickness.
Comparative example 1
The lithium manganate matrix material described in example 1.
Comparative example 2
S1: manganese oxide and lithium hydroxide are mixed according to the molar ratio of manganese element to lithium element of 2:1, premixing and preheating, wherein the preheating temperature is 400 ℃, the presintering time is 4 hours, and grinding a sintered product to obtain a product 1;
s2: stannous sulfate and sucrose are mixed according to a mole ratio of 1:1, preparing a suspension 2;
s3: according to the mole ratio of tin element to lithium element of 0.02:1, adding the product 1 into the suspension 2, uniformly mixing, transferring into a hydrothermal kettle, and reacting for 10 hours at 200 ℃;
s4: and filtering the reaction product, washing the reaction product with deionized water for 3 times, drying the washed product, and calcining the dried product at 700 ℃ for 7 hours under the protection of inert gas to finally obtain the tin oxide coated lithium manganate positive electrode material.
Fig. 2 is a scanning electron microscope image of a nano lithium nickelate coated modified lithium manganate material prepared in example 1, and fig. 3 is a scanning electron microscope image of a lithium manganate matrix of comparative example 1. As can be seen from fig. 2, the spherical lithium manganate prepared in example 1 has a smooth surface and no obvious pore structure; as can be seen from fig. 3, the lithium manganate matrix prepared in comparative example 1 has a rough surface and a large number of pore structures between primary particles.
Table 1 shows the specific surface areas of examples 1 to 8 and comparative examples 1 and 2. As can be seen from Table 1, the specific surface areas of examples 1 to 10 are significantly smaller than those of comparative examples 1 and 2.
Table 1 comparative tables of specific surface areas of examples 1 to 8 and comparative examples 1 and 2
Figure BDA0004095752440000111
The products of examples 1 to 8, comparative example 1 and comparative example 2 were used as positive electrode materials, and metallic lithium was used as negative electrode, and button lithium ion batteries were fabricated and tested.
Table 2 is a table showing the first efficiencies and specific discharge capacities of the batteries fabricated in examples 1 to 8 and comparative examples 1 and 2. As can be seen from table 2, the first efficiency and specific discharge capacity of the batteries fabricated in examples 1 to 8 were significantly better than those of comparative examples 1 and 2.
Table 2 first efficiency and specific discharge capacity comparison tables for batteries prepared in examples 1 to 8 and comparative example 1 and comparative example 2
Figure BDA0004095752440000112
The normal temperature cycle performance of the lithium ion battery was tested, and the results are shown in fig. 4, and fig. 4 is a graph showing the first coulombic efficiency and the first charge-discharge specific capacity of the battery prepared in example 1, comparative example 1 and comparative example 2. As can be seen from fig. 4, the 0.2C discharge specific capacity of the battery fabricated in example 1 was 129.5mAh/g, and the initial coulombic efficiency was 96.5%; comparative example 1 a battery was produced with a 0.2C discharge specific capacity of 123.5mAh/g and a first coulombic efficiency of 95.6%; comparative example 2 a battery with a 0.2C discharge specific capacity of 107.2mAh/g and a first coulombic efficiency of 93.5%; the initial coulombic efficiency and specific discharge capacity of example 1 were both superior to those of comparative examples 1 and 2.
The 1C normal temperature cycle performance of the fabricated lithium ion battery was tested, and the results are shown in fig. 5, and fig. 5 is a graph comparing the 1C normal temperature cycle performance of the fabricated batteries of example 1, comparative example 1 and comparative example 2. As can be seen from fig. 5, the specific discharge capacity of example 1 battery 1C was 127.5mAh/g, and the capacity retention rate at 50 cycles was 94.9%; comparative example 1 a battery was fabricated with a 1C discharge specific capacity of 123.3mAh/g and a 50-cycle capacity retention of 81.8%; comparative example 2 battery 1C has a specific discharge capacity of 106mAh/g and a 50-cycle capacity retention of 89.4%; the normal temperature cycle performance of example 1 is superior to that of comparative examples 1 and 2.
The high temperature cycle performance at 55 ℃ of the prepared lithium ion battery is tested, and the result is shown in fig. 6, and fig. 6 is a graph comparing the high temperature cycle performance at 55 ℃ of the batteries prepared in example 1, comparative example 1 and comparative example 2. As can be seen from fig. 6, the specific discharge capacity of example 1 battery 1C was 126.8mAh/g, and the capacity retention rate at 50 cycles was 87.4%; comparative example 1 produced a battery with a 1C discharge specific capacity of 123.4mAh/g and a 50-cycle capacity retention of 78.8%; comparative example 2 battery 1C has a specific discharge capacity of 108.3mAh/g and a 50-cycle capacity retention of 80.2%; the method comprises the steps of carrying out a first treatment on the surface of the The high temperature cycle performance of example 1 is superior to that of comparative examples 1 and 2.
The products of examples 1 to 8, comparative example 1 and comparative example 2 were used as positive electrode materials, and artificial graphite was used as a negative electrode, and a 10Ah soft pack lithium ion battery was fabricated and tested.
Table 3 shows a comparison table of the test results of the 55 ℃ C./14-day high-temperature storage of the batteries produced in examples 1 to 8 and comparative examples 1 and 2. As can be seen from table 3, the high-temperature storage performance, capacity recovery rate, and dissolution of manganese in the negative electrode of the batteries fabricated in examples 1 to 8 were significantly better than those of comparative examples 1 and 2.
Table 3 comparative tables of test results of 55 ℃/14 day high temperature storage of batteries fabricated in examples 1 to 8 and comparative examples 1 and 2
Figure BDA0004095752440000121
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. The nano lithium nickelate coated modified lithium manganate anode material is characterized by comprising a lithium manganate matrix formed by aggregation of primary particles and a nano lithium nickelate layer coated on the surface of the lithium manganate matrix, wherein the nano lithium nickelate layer is continuously coated on the surface of the lithium manganate matrix, and the nano lithium nickelate is filled in pores among the primary particles on the surface of the lithium manganate matrix in a wedge-shaped form.
2. The positive electrode material according to claim 1, wherein the thickness of the nano lithium nickelate layer is 10-800 nm, and the nano lithium nickelate layer is coated on the surface of the lithium manganate matrix continuously with non-uniform thickness.
3. The positive electrode material according to claim 1, wherein the positive electrode material has a specific surface area of 0.1 to 0.5m 2 /g。
4. The preparation method of the nano lithium nickelate coated modified lithium manganate positive electrode material is characterized by comprising the following steps of:
a) Adding a lithium manganate matrix into a mixed solution of a surfactant and a dispersing agent, and mixing to obtain a surfactant-coated lithium manganate matrix I, wherein the surfactant is selected from water-insoluble or slightly water-soluble organic carboxylic acid;
b) Adding the lithium manganate matrix I wrapped by the surfactant into a nickel salt aqueous solution, mixing, and aging to obtain a lithium manganate matrix II;
c) And mixing the lithium source compound with a lithium manganate matrix II, and sintering to obtain the nano lithium nickelate coated modified lithium manganate anode material.
5. The method according to claim 4, wherein the surfactant is one or more selected from the group consisting of benzoic acid, phthalic acid, caproic acid, enanthic acid, caprylic acid, isooctanoic acid, pelargonic acid, capric acid, palmitic acid, oleic acid, and stearic acid.
6. The preparation method according to claim 4, wherein the dispersing agent is one or more selected from ethanol, diethyl ether, acetone, chloroform and pyridine;
the mass ratio of the surfactant to the dispersant is 0.01-5: 1.
7. the method according to claim 4, wherein the nickel salt is one or more selected from the group consisting of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate;
the molar concentration of the nickel salt aqueous solution is 1-6 mol/L.
8. The method according to claim 4, wherein the lithium source compound is one or more selected from the group consisting of lithium carbonate, lithium hydroxide, and lithium nitrate;
the mass ratio of the lithium source compound to the lithium manganate matrix II is 0.005-0.1: 1.
9. the method according to claim 2, wherein the aging time is 0.5 to 12 hours;
the sintering temperature is 600-850 ℃, and the sintering time is 2-12 h.
10. A lithium ion battery, characterized by comprising the nano lithium nickelate coated modified lithium manganate positive electrode material according to any one of claims 1 to 3 or the nano lithium nickelate coated modified lithium manganate positive electrode material prepared by the preparation method according to any one of claims 4 to 9.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN106328888A (en) * 2015-07-10 2017-01-11 北京当升材料科技股份有限公司 Novel lithium cobalt oxide positive electrode material and preparation method therefor
CN109360951A (en) * 2018-09-21 2019-02-19 郑忆依 A kind of preparation method of modified nickel ion doped
CN111193007A (en) * 2020-02-28 2020-05-22 浙江克能新能源科技有限公司 Lithium manganate material battery positive electrode and preparation method thereof, and lithium manganate battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106328888A (en) * 2015-07-10 2017-01-11 北京当升材料科技股份有限公司 Novel lithium cobalt oxide positive electrode material and preparation method therefor
CN109360951A (en) * 2018-09-21 2019-02-19 郑忆依 A kind of preparation method of modified nickel ion doped
CN111193007A (en) * 2020-02-28 2020-05-22 浙江克能新能源科技有限公司 Lithium manganate material battery positive electrode and preparation method thereof, and lithium manganate battery

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