CN111463410B - Positive electrode material, and preparation method and application thereof - Google Patents

Positive electrode material, and preparation method and application thereof Download PDF

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CN111463410B
CN111463410B CN201910057997.7A CN201910057997A CN111463410B CN 111463410 B CN111463410 B CN 111463410B CN 201910057997 A CN201910057997 A CN 201910057997A CN 111463410 B CN111463410 B CN 111463410B
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praseodymium
electrode material
lithium
positive electrode
source
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CN111463410A (en
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郑玉
严武渭
杨顺毅
黄友元
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BTR Nano Tech Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a positive electrode material which comprises a base material and lithium praseodymium oxide distributed on the surface of the base material and among primary particles of the base material. The chemical general formula of the matrix material is Li z Ni 1‑x‑y Co x M y O 2 X is more than or equal to 0 and less than or equal to 0.35,0 and less than or equal to 0.6,0.95 and less than or equal to 1.30, and M is any one or combination of at least two of Mn, al, V, mg, mo, nb and Ti. The chemical formula of the praseodymium lithium is Li a PrO b 2-a-4, wherein the molar weight of praseodymium element in the praseodymium lithium is 0.05-2.00 percent to 1 of the total molar weight of Ni, co and M elements in the matrix material. According to the invention, the lithium praseodymium oxide is distributed on the surface of the matrix material and among primary particles of the matrix material, so that the positive electrode material is endowed with good electrochemical performance, and the capacity retention rate of 50 cycles is more than or equal to 91.6% under the current density of 1C.

Description

Positive electrode material, and preparation method and application thereof
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a positive electrode material, and a preparation method and application thereof.
Background
The intelligent equipment is diversified, and the development of the lithium ion battery is effectively promoted. Meanwhile, the vigorous development of the new energy automobile industry opens up a new blue sea for the application of lithium ion batteries. However, the duration trouble seriously affects the consumption experience. In order to be more marketable, the energy density of lithium ion batteries must be continuously increased.
Conventionally, the energy density of lithium ion batteries has been mainly limited by the positive electrode material. Currently, the most mature path to increase the energy density of lithium ion batteries is to accelerate the commercial application of ternary cathode materials, particularly high nickel ternary cathode materials. However, the ternary cathode material has problems in practical applications, and among them, the relatively troublesome problem is that the cycle is poor, and the reasons are mainly as follows: 1. secondary spherical particles are broken due to repeated expansion and contraction changes of the volume of the anode material in charge-discharge cycles; 2. the surface of the anode material with high reactivity has side reaction with the electrolyte, a passivation layer is generated on the surface, and the electrolyte is consumed; 3. the layered structure of the anode material is gradually transformed into a rock salt structure; 4. the reactive metal ions in the positive electrode material are dissolved in the electrolyte.
CN103855384B discloses a rare earth doped modified lithium ion battery ternary anode material and a preparation method thereof, and the chemical general formula of the material is as follows: liNi a Co 1-a-b Mn b R x O 2 /M, wherein 0<a<1，0<b<1，0<1-a-b<1，0.005<x<0.1, R is one or more of rare earth lanthanum, cerium, praseodymium and samarium, and M is a composite coating layer of an oxide of aluminum, titanium or magnesium and carbon. The preparation method comprises the following steps: soluble metal nickel salt, cobalt salt, manganese salt and rare earth compound are prepared into mixed salt solution, the mixed salt solution reacts with mixed alkali solution prepared from NaOH and ammonia water, the mixed solution is filtered, washed and dried, then the mixed solution is evenly mixed with lithium salt powder by ball milling, and the mixture is coated with a composite coating layer containing aluminum, titanium or magnesium oxide and carbon by high-temperature calcination and then is prepared by constant-temperature calcination. The method has complex preparation process and cannot meet the requirement of industrial production.
CN107579224a discloses a method for preparing a nickel-cobalt-manganese ternary material doped with rare earth ions, which is characterized in that the rare earth ion-doped compound is an oxide, nitrate, oxalate, chloride or carbonate of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, yttrium or scandium. Mixing compounds of nickel, cobalt, manganese and rare earth ions, and preparing a dried precursor through the steps of wet grinding, adding ammonia water, adding a lithium compound, aging, drying and the like. And (3) placing the dried precursor in oxygen-enriched air or pure oxygen atmosphere, and preparing the rare earth ion-doped ternary cathode material by adopting a programmed heating method or a temperature-zone-by-temperature-zone heating method, wherein the cycle performance of the material is poor.
CN103872325B discloses a preparation method of praseodymium, cobalt and phosphorus doped lithium manganese silicate composite positive electrode material, and the praseodymium, cobalt and phosphorus doped manganese silicateThe chemical formula of lithium is LiMn 1-x-y Co x Pr y Si 1-z P z O 4 Wherein: x is 0.2-0.25, y is 0.01-0.02, and z is 0.22-0.34. The preparation method comprises the following steps: preparing a praseodymium-cobalt-phosphorus-doped lithium manganese silicate precursor; (2) Crushing after heat treatment to obtain precursor powder, dispersing carbon black and active carbon into acetone to form conductive carbon dispersion liquid, mixing the precursor powder with the conductive carbon dispersion liquid, and ball-milling the mixture; (3) Drying, and placing in CO/CO solution at a molar ratio of 1:1 2 And blowing the mixture into an intermittent converter, sintering, grinding and sieving to obtain the product. According to the praseodymium, cobalt and phosphorus doped manganese lithium silicate composite anode material prepared by the invention, rare earth elements Pr and metal elements Co are doped in the manganese lithium silicate to modify Mn, and P is used for replacing part of Si to improve the electronic conductivity and the material activity. The method has complex preparation process and cannot meet the requirement of industrial production.
Therefore, there is a need in the art to develop a cathode material that has good electrochemical properties, is simple in preparation process, and can be industrially produced.
Disclosure of Invention
In view of the shortcomings of the prior art, one of the objectives of the present invention is to provide a positive electrode material, which comprises a matrix material and lithium praseodymium oxide distributed on the surface of the matrix material and among primary particles of the matrix material.
In the prior art, the coating obtained by adopting a coating method is mainly distributed on the surface of the secondary particles of the material, so that the fracture of the secondary particles is not inhibited, and meanwhile, the conductivity of the coating is low, so that the diffusion of lithium ions is hindered, and the discharge specific capacity or the rate capability is reduced.
According to the invention, the lithium praseodymium oxide is distributed on the surface of the base material and among the primary particles of the base material, and has good conductivity, so that the positive electrode material can be endowed with good electrochemical performance, and is filled among the primary particles, and the connection among the primary particles is enhanced, thereby inhibiting the fragmentation of the secondary particles.
In the invention, the lithium praseodymium oxide can physically isolate the positive active material from the electrolyte, so that the surface side reaction and the dissolution of the reaction metal ions are reduced, meanwhile, the lithium praseodymium oxide can also prevent the problem of electrode pulverization caused by repeated expansion and contraction change of the volume of the material in the charge-discharge cycle, and further improve the cycle performance of the positive material, and the capacity retention rate of the positive material after 50 cycles is more than or equal to 91.6 percent under the current density of 1C.
Preferably, the chemical formula of the matrix material is Li z Ni 1-x-y Co x M y O 2 Preferably 0. Ltoreq. X.ltoreq. 0.35,0. Ltoreq. Y.ltoreq. 0.6,0.95. Ltoreq. Z.ltoreq.1.30, M is any one or a combination of at least two of Mn, al, V, mg, mo, nb and Ti.
Preferably, 0 ≦ x ≦ 0.35, such as 0.1, 0.15, 0.2, 0.25, 0.3, and so forth.
Preferably, 0. Ltoreq. Y.ltoreq.0.6, such as 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, etc.
Preferably, said 0.95. Ltoreq. Z.ltoreq.1.30, such as 1.0, 1.05, 1.10, 1.15, 1.20, 1.25, etc.
Preferably, M is any one or a combination of at least two of Mn, al, V, mg, mo, nb, and Ti, such as Mn, al, V, and the like.
Preferably, the chemical formula of the lithium praseodymium is Li a PrO b Preferably 2. Ltoreq.2b-a. Ltoreq.4, e.g.2, 3, 4 etc.
Preferably, the ratio of the molar amount of praseodymium element in the lithium praseodymium to the total molar amount of Ni, co and M elements in the base material is 0.05-2.00%: 1, such as 0.06%:1, 0.13%:1, 0.38%:1, 0.53%:1, 1.01%:1, etc.
It is obvious to those skilled in the art that the total molar amount of the Ni element, the Co element, and the M element in the matrix material of the present invention represents the total molar amount of the Ni element and the M element when x is 0; when y is 0, the total molar amount of Ni element and Co element is represented; when x and y are 0 respectively, the total molar amount of Ni element is represented; when x + y is 1, it represents the total molar amount of Co element and M element.
The invention also aims to provide a preparation method of the cathode material, which comprises the following steps:
(1) Washing the first electrode material with water, and performing solid-liquid separation to obtain a solid-phase washing product;
(2) Mixing the water washing product with a praseodymium source, and drying to obtain a pre-product;
(3) And carrying out heat treatment on the pre-product in a heat treatment atmosphere to obtain the anode material.
In the prior art, after the ternary cathode material is synthesized, li is remained in the material, and the part of Li is generally LiOH and Li 2 CO 3 The form of (b) is present, and further the impedance of the positive electrode active material is increased, and the problem of gas generation of the material is caused. LiOH and Li are used herein 2 CO 3 Li contained in (1) + Collectively referred to as free Li + H consumption measured by chemical titration + Free Li can be calculated + And (4) content.
The invention converts free Li + Washing the first electrode material with higher content with water to reduce the content of free Li in the material, and washing the first electrode material with water to obtain the residual free Li + Will react with LiOH and Li 2 CO 3 Is mixed with a praseodymium source to prepare the praseodymium lithium distributed on the surface of the matrix material and among primary particles of the matrix material.
Preferably, the free Li of the first electrode material in step (1) of the present invention + The content is 0.2 to 2% by weight, for example, 0.25%, 0.3%, 0.35%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% and the like.
Preferably, the first electrode material includes any one or a combination of at least two of Ni element, co element, and M element, which is any one or a combination of at least two of Mn element, al element, V element, mg element, mo element, nb element, and Ti element.
The first electrode material is washed by water and mixed with a praseodymium source to remove free Li according to the method + Drying and heat treatment to obtain the matrix material in the cathode materialThe chemical general formula of the material is Li z Ni 1-x- y Co x M y O 2 Preferably, x is 0. Ltoreq. X.ltoreq. 0.35,0. Ltoreq. Y.ltoreq. 0.6,0.95. Ltoreq. Z.ltoreq.1.30, and M is any one or a combination of at least two of Mn, al, V, mg, mo, nb, and Ti.
Preferably, the temperature of the water washing is 10 to 40 ℃, for example, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃ and the like.
Preferably, the time of the water washing is 5 to 50min, such as 10min, 20min, 30min, 40min and the like.
Preferably, the mass ratio of the first electrode material to water in the water washing process is 0.5-4:1, for example, 1:1, 1.5.
Preferably, the water content in the water-washed product is 5 to 15wt%, such as 7wt%, 8wt%, 10wt%, 12wt%, 14wt%, etc.
The water content of the washing product is 5-15 wt%, so that praseodymium source can be better dispersed and infiltrated between the surface of the first electrode material and primary particles after washing.
Preferably, the water-washed product of step (2) contains free Li + The molar ratio of the praseodymium element in the praseodymium source is 1.0 to 8.0, and for example, 2.0.
Free Li + When the molar ratio of the medium lithium element to the praseodymium element in the praseodymium source is more than 8.0, the remaining free Li + More, and further in the electrochemical reaction process, the impedance of the positive active material may be increased and the gas generation problem is aggravated, resulting in poor electrochemical performance of the material; free Li + If the molar ratio of the medium lithium element to the praseodymium element in the praseodymium source is less than 1:1, the praseodymium element will generate praseodymium oxide, resulting in poor ion conductivity.
Preferably, the mixing mode of the washing product and the praseodymium source is ball milling mixing or stirring mixing.
Preferably, the praseodymium source includes any one or a combination of at least two of praseodymium oxide, praseodymium nitrate and praseodymium carbonate.
Preferably, the drying temperature is 60 to 90 ℃, such as 65 ℃,70 ℃, 75 ℃, 80 ℃, 85 ℃ and the like.
According to the invention, the water evaporation rate of the material is strictly controlled in the drying process, so that the dispersibility of the praseodymium source between the surface of the positive electrode material and primary particles is good, the drying temperature is less than 60 ℃, the water evaporation of the material is too slow, the reaction time is longer, and the industrial production is influenced; the drying temperature is higher than 90 ℃, the water in the material is evaporated too fast, and the dispersibility of the praseodymium source between the surface of the anode material and primary particles is poor.
Preferably, the drying time is 0.5 to 5 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, and the like.
Preferably, the temperature of the heat treatment in step (3) is 500 to 700 ℃, for example 550 ℃,600 ℃, 650 ℃, and the like.
Preferably, the heat treatment time is 5 to 15 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours and the like.
Preferably, the heat treatment atmosphere includes an oxygen atmosphere or a decarbonated air atmosphere.
The decarbonated air atmosphere in the present invention means an atmosphere obtained by removing carbon dioxide from air.
The invention controls the content of carbon dioxide in the atmosphere during the heat treatment process so as to prevent the carbon dioxide and the electrode material from generating new Li 2 CO 3 By-products.
As one of preferable technical solutions, the preparation method of the cathode material of the present invention includes the following steps:
(1) According to the mass ratio of the first electrode material to the water of 0.5-4:1, dissociating Li + Washing the first electrode material with the content of 0.2-2 wt% for 5-50 min at the temperature of 10-40 ℃, and performing solid-liquid separation to obtain a solid-phase washing product with the water content of 5-15 wt%;
(2) Ball-milling and mixing the water washing product with a praseodymium source, wherein free Li is contained in the water washing product + The molar ratio of the precursor to praseodymium element in a praseodymium source is 1.0-8.0, and the precursor is dried at the temperature of 60-90 ℃ for 0.5-5 h to obtain a pre-product;
(3) And carrying out heat treatment on the pre-product for 5-15 h at 500-700 ℃ in an oxygen atmosphere to obtain the anode material.
The invention also aims to provide a preparation method of the cathode material, which comprises the following steps:
(1) Dissolving a praseodymium source and a lithium source in water to prepare a mixed solution;
(2) Adding the mixed solution into a second electrode material to obtain an electrode material mixed solution, and drying to obtain a pre-product;
(3) And carrying out heat treatment on the pre-product in a heat treatment atmosphere to obtain the cathode material.
Free Li in the second electrode material of the invention + The content is less, so a praseodymium source and a lithium source are added into the second electrode material in a mode of adding the praseodymium source and the lithium source to prepare the cathode material.
According to the invention, the mixed solution containing the praseodymium source and the lithium source is mixed with the second electrode material solution, so that the praseodymium source and the lithium source are better dispersed and infiltrated between the surface of the second electrode material and primary particles.
Preferably, the second electrode material of step (2) of the present invention contains free Li + The content is < 0.2wt%, such as 0.01wt%, 0.05wt%, 0.12wt%, 0.15wt%, etc.
Preferably, in the step (1), the molar ratio of the lithium element in the lithium source to the praseodymium element in the praseodymium source is 1.0 to 8.0, for example, 2.0.
Preferably, the mass ratio of the total mass of the praseodymium source and the lithium source to the water is 0.1 to 5:1, for example, 0.5.
Preferably, the praseodymium source includes any one or a combination of at least two of praseodymium oxide, praseodymium nitrate and praseodymium carbonate, such as praseodymium nitrate, praseodymium carbonate, and the like.
The praseodymium source does not generate impurities which are difficult to decompose after being introduced.
Preferably, the lithium source includes any one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate and lithium oxalate or a combination of at least two thereof, for example, lithium hydroxide, lithium carbonate, lithium nitrate and the like.
Preferably, the second electrode material includes any one or a combination of at least two of Ni element, co element, and M element, and the M element is any one or a combination of at least two of Mn element, al element, V element, mg element, mo element, nb element, and Ti element.
According to the preparation method, the second electrode material is dried, thermally treated and the like to obtain the matrix material in the anode material, wherein the chemical general formula of the matrix material is Li z Ni 1-x-y Co x M y O 2 Preferably, x is 0. Ltoreq. X.ltoreq. 0.35,0. Ltoreq. Y.ltoreq. 0.6,0.95. Ltoreq. Z.ltoreq.1.30, and M is any one or a combination of at least two of Mn, al, V, mg, mo, nb, and Ti.
Preferably, the ratio of the praseodymium element in the electrode material mixture in step (2) to the total molar amount of the Ni element, co element and M element in the second electrode material is 0.05% -2% to 1, such as 0.08% to 1, 0.1% to 1, 0.25% to 1, 0.5% to 1, 1% to 1, 1.2% to 1, 1.5% to 1, 1.8% to 1, and so on.
The total molar weight of Ni element, co element and M element in the second electrode material represents the total molar weight of Ni element and M element when the content of Co element in the second electrode material is 0; when the content of the M element in the second electrode material is 0, the total molar quantity of the Ni and the Co elements is represented; when the contents of Co element and M element in the second electrode material are respectively 0, the Ni element represents the molar weight; when the content of the Ni element is 0, it represents the total molar amount of the Co element and the M element.
Preferably, the mass ratio of the mixed solution to the second electrode material in step (2) is from 0.05 to 0.15, for example, from 0.06.
Preferably, the drying temperature is 60 to 90 ℃, such as 65 ℃,70 ℃, 75 ℃, 80 ℃, 85 ℃ and the like.
The drying temperature is less than 60 ℃, the evaporation of the water in the material is too slow, the reaction time is longer, and the industrial production is influenced; the drying temperature is higher than 90 ℃, the water in the material is evaporated too fast, and the dispersibility of the praseodymium source between the surface of the anode material and primary particles is poor.
The invention strictly controls the drying rate so as to ensure that the praseodymium source has good dispersibility on the surface of the cathode material and between primary particles.
Preferably, the drying time is 0.5 to 5 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, and the like.
Preferably, the temperature of the heat treatment in step (4) is 500 to 700 ℃, such as 550 ℃,600 ℃, 650 ℃, and the like.
Preferably, the heat treatment time is 5 to 15 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours and the like.
Preferably, the heat treatment atmosphere includes an oxygen atmosphere or a decarbonated air atmosphere.
The invention strictly controls the content of carbon dioxide in the atmosphere in the heat treatment process, and avoids the regeneration of a byproduct Li 2 CO 3 。
As a second preferred technical solution, the preparation method of the positive electrode material of the present invention comprises the following steps:
(1) Dissolving a praseodymium source and a lithium source in water according to the molar ratio of the lithium element in the lithium source to the praseodymium element in the praseodymium source of 1.0-8.0 to prepare a mixed solution;
(2) According to the mass ratio of the mixed liquid to the second electrode material of 0.05-0.15 + Adding a second electrode material with the content of less than 0.2wt% into the mixed solution, and drying at the temperature of between 60 and 90 ℃ for 0.5 to 5 hours to obtain a pre-product;
(3) And carrying out heat treatment on the pre-product for 5-15 h at 500-700 ℃ in an oxygen atmosphere to obtain the anode material.
The invention also provides the use of the positive electrode material as one of the purposes, and the positive electrode material is applied to the field of batteries, preferably the field of positive electrode materials of lithium ion batteries.
The fifth purpose of the invention is to provide a lithium ion battery, which comprises the cathode material of one purpose.
Preferably, the lithium ion positive electrode material is one of the positive electrode materials described above.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the lithium praseodymium oxide is distributed on the surface of the matrix material and among primary particles of the matrix material, so that the positive electrode material is endowed with good electrochemical performance, and the capacity retention rate of the positive electrode material after 50 cycles is more than or equal to 91.6% under the current density of 1C.
(2) The invention converts free Li + Washing the first electrode material with higher content to reduce the content of free Li in the material and the residual free Li + Mixing with a praseodymium source to prepare praseodymium lithium distributed on the surface of the base material and among primary particles of the base material; the invention is in free Li + The second electrode material with low content adopts a mode of adding a praseodymium source and a lithium source, and the praseodymium source and the lithium source are added into the second electrode material, so that the prepared positive electrode material has good electrochemical performance.
(3) In a further preferable technical scheme, the method controls the free Li in the first electrode material after water washing by controlling the temperature and time of water washing + Content, elimination of excess free Li + Thereby reducing the impedance of the anode material; the water content of the product of water washing is kept to be 5-15 wt%, so that praseodymium sources can be better dispersed and infiltrated into the surface of the first electrode material after water washing and primary particles, and the cycle performance of the material is improved; the invention strictly controls the water evaporation rate of the material in the drying process, thereby ensuring that the praseodymium source has good dispersibility between the surface of the anode material and primary particles, and further improving the cycle performance of the material.
Drawings
Fig. 1 is an SEM image of the positive electrode material obtained in example 1 of the present invention.
Fig. 2 is an SEM image of the positive electrode material obtained in comparative example 1 of the present invention.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the cathode material comprises the following steps:
(1) According to LiNi 0.8 Co 0.1 Mn 0.1 O 2 LiNi with a free Li content of 0.5wt% in a mass ratio to water of 3.4 0.8 Co 0.1 Mn 0.1 O 2 Washing at 30 deg.C for 30min, and performing solid-liquid separation to obtain solid-phase washing product with water content of 10 wt%;
(2) Mixing the water-washed product with Pr 2 O 3 Ball milling and mixing, and washing the free Li in the product + And Pr 2 O 3 The molar ratio of medium praseodymium element is 4.0, and the pre-product is obtained after drying for 4h at 70 ℃;
(3) And (2) carrying out heat treatment on the pre-product at 600 ℃ for 10h in an oxygen atmosphere to obtain a positive electrode material, wherein the molar weight of praseodymium element in the positive electrode material and the total molar weight of Ni, co and Mn elements in the matrix material are 0.13%:1, and an SEM image of the positive electrode material is shown in figure 1, wherein the positive electrode material has uniform particle size distribution, the particle size is 10-20 mu m, and the surface is provided with a coating layer.
Example 2
The difference from example 1 is that the product of step (2) is washed with water to remove free Li + And Pr 2 O 3 The molar ratio of the praseodymium element in the positive electrode material is 1.0, and the molar ratio of the praseodymium element in the positive electrode material to the total molar amount of the Ni, co and Mn elements in the matrix material is 0.52%:1.
Example 3
The difference from example 1 is that the product of step (2) is washed with water to remove free Li + And Pr 2 O 3 The molar ratio of the praseodymium element in the positive electrode material is 8.0 to 1, and the molar ratio of the molar amount of the praseodymium element in the positive electrode material to the total molar amount of the Ni, co and Mn elements in the matrix material is 0.06 to 1.
Example 4
The difference from example 1 is that the product of step (2) is washed with water to remove free Li + And Pr 2 O 3 The molar ratio of the praseodymium element in the positive electrode material is 0.5 to 1, and the molar ratio of the molar amount of the praseodymium element in the positive electrode material to the total molar amount of the Ni, co and Mn elements in the matrix material is 1.01 to 1.
Example 5
The difference from example 1 is that the product of step (2) is washed with water to remove free Li + And Pr 2 O 3 The molar ratio of the praseodymium element in the positive electrode material is 9.0 to 1, and the molar ratio of the molar amount of the praseodymium element in the positive electrode material to the total molar amount of the Ni, co and Mn elements in the matrix material is 0.06 to 1.
Example 6
The preparation method of the cathode material comprises the following steps:
(1) In terms of LiNi 0.8 Co 0.1 Al 0.1 O 2 The mass ratio of the free Li to the water is 4:1 + LiNi in an amount of 0.35wt% 0.8 Co 0.1 Al 0.1 O 2 Washing at 10 deg.C for 50min, and performing solid-liquid separation to obtain solid-phase washing product with water content of 5 wt%;
(2) Ball-milling and mixing the water washing product with praseodymium nitrate, wherein free Li is contained in the water washing product + The molar ratio of the precursor to praseodymium element in praseodymium nitrate is 4.0, and the precursor is obtained after drying for 5 hours at 60 ℃;
(3) And (3) carrying out heat treatment on the pre-product for 15h at 500 ℃ in an oxygen atmosphere to obtain a positive electrode material, wherein the molar weight ratio of praseodymium to the total molar weight of Ni, co and Al elements in the matrix material is 0.09%:1.
Example 7
The preparation method of the cathode material comprises the following steps:
(1) According to LiNi 0.8 Co 0.1 Al 0.1 O 2 The mass ratio of the free Li to the water is 4:1 + LiNi in an amount of 0.35wt% 0.8 Co 0.1 Al 0.1 O 2 Washing for 50min at 10 ℃, and carrying out solid-liquid separation to obtain a solid-phase washing product with the water content of 5 wt%;
(2) Ball-milling and mixing the water washing product with praseodymium nitrate, wherein free Li is contained in the water washing product + The molar ratio of the praseodymium nitrate to the praseodymium element in the praseodymium nitrate is 1:1, and a pre-product is obtained after drying for 5 hours at 60 ℃;
(3) And (3) carrying out heat treatment on the pre-product for 15h at 500 ℃ in an oxygen atmosphere to obtain a positive electrode material with the molar weight of praseodymium element and the total molar weight of Ni, co and Al elements in the matrix material being 0.38% to 1.
Example 8
The preparation method of the cathode material comprises the following steps:
(1) According to the lithium element and Pr in the lithium hydroxide 2 O 3 The molar ratio of praseodymium element in the material is 4.0 2 O 3 And lithium hydroxide are dissolved in water to prepare a mixed solution;
(2) According to a mixture of 0.6 Co 0.2 Mn 0.2 O 2 Is 0.1, 1,Pr 2 O 3 Medium praseodymium element and LiNi 0.6 Co 0.2 Mn 0.2 O 2 The total molar weight of Ni, co and Mn is 0.1%:1, and free Li is added + LiNi in an amount of 0.1wt% 0.6 Co 0.2 Mn 0.2 O 2 Adding the mixture into the mixed solution, and drying the mixture for 3 hours at 70 ℃ to obtain a pre-product;
(3) And carrying out heat treatment on the pre-product for 10h at 600 ℃ in an oxygen atmosphere to obtain the anode material.
Example 9
The difference from example 8 is that lithium and Pr are present in lithium hydroxide in step (1) 2 O 3 The molar ratio of medium praseodymium element is 1.0.
Example 10
The difference from example 8 is that lithium element and Pr in the lithium hydroxide of step (1) 2 O 3 The molar ratio of the medium praseodymium element is 8.0.
Example 11
The difference from example 8 is that lithium and Pr are present in lithium hydroxide in step (1) 2 O 3 The molar ratio of the medium praseodymium element is 0.5.
Example 12
The difference from example 8 is that lithium and Pr are present in lithium hydroxide in step (1) 2 O 3 The molar ratio of medium praseodymium element is 9.0.
Example 13
Differs from example 8 in the step (2) Pr 2 O 3 Medium praseodymium element and LiNi 0.6 Co 0.2 Mn 0.2 O 2 Medium Ni element, CThe total molar weight ratio of the o element and the Mn element is 0.05 percent to 1.
Example 14
Differs from example 8 in the step (2) Pr 2 O 3 Medium praseodymium element and LiNi 0.6 Co 0.2 Mn 0.2 O 2 The total molar weight ratio of Ni element, co element and Mn element is 0.5% to 1.
Example 15
Differs from example 8 in the step (2) Pr 2 O 3 Medium praseodymium element and LiNi 0.6 Co 0.2 Mn 0.2 O 2 The total molar weight ratio of Ni element, co element and Mn element is 1% to 1.
Example 16
Differs from example 8 in the step (2) Pr 2 O 3 Medium praseodymium element and LiNi 0.6 Co 0.2 Mn 0.2 O 2 The ratio of the total molar weight of Ni element, co element and Mn element is 2% to 1.
Comparative example 1
The difference from example 1 is that in step (2), no Pr was added 2 O 3 The SEM image of the prepared cathode material is shown in FIG. 2, and it can be seen that the cathode material is easy to agglomerate to generate large particles with the particle size of 10-40 μm, and the surface has no coating layer.
Comparative example 2
The difference from example 8 is that no Pr was added in step (1) 2 O 3 。
Comparative example 3
The preparation method of the cathode material comprises the following steps:
(1) The nickel salt, the cobalt salt, the manganese salt and the praseodymium salt are mixed according to the metal molar ratio of 0.75. Mixing a mixed salt solution, a 2mol/L precipitator NaOH solution and a complexing agent NH 3 ·H 2 The O solution is cocurrent flowed with the three, added into a reactor which takes NaOH solution with pH of 11.25 as base solution, the pH is controlled to be kept at 11.25 plus or minus 0.05 all the time, stirred and reacted for 24 hours at 50 ℃, overflowed to obtain product slurry, the product slurry is aged for 20 hours, and filtered to obtain Ni 0.75 Co 0.1 Mn 0.1 Pr 0.05 (OH) 2 A multi-element precursor;
(2) Mixing the multi-element precursor with LiOH according to the metal molar ratio of 1.05;
(4) Grinding and screening the crude product to obtain a monocrystal-like multi-component material finished product with a chemical formula of Li 1.02 Ni 0.75 Co 0.1 Mn 0.1 Pr 0.05 O 2 。
And (3) performance testing:
the prepared positive electrode material is subjected to the following performance tests:
(1) Assembling the battery: the anode material prepared by the invention is prepared into an anode plate, the cathode is a metal lithium plate, the diaphragm is Celgard2400, and the electrolyte is 1mol/L LiPF 6 and/DMC + DEC, assembling to obtain CR2025 button cell. The preparation process of the positive pole piece comprises the following steps: mixing the prepared positive electrode material, acetylene black as a conductive agent and PVDF (polyvinylidene fluoride) as a binder according to the mass ratio of 90.
(2) Electrochemical testing: and (3) testing the prepared button cell on a LAND cell testing system of Wuhanjinuo electronic Limited company under the condition of normal temperature, wherein the charging and discharging voltage interval is 3.0-4.3V, and the current density of 1C is defined to be 200mA/g. The 50-cycle retention ratio = 50-cycle specific discharge capacity/specific first discharge capacity, in the table, 0.1C/0.1C represents the specific first discharge capacity when the battery is charged to the charge cut-off voltage at the current density of 0.1C and discharged to the discharge cut-off voltage at the current density of 0.1C; 0.5C/0.5C represents the specific capacity of the initial discharge when the charge is carried out to the charge cut-off voltage under the current density of 0.5C and the discharge is carried out to the discharge cut-off voltage under the current density of 0.5C; 0.5C/1C represents the specific capacity of the initial discharge when the battery is charged to the charge cut-off voltage at the current density of 0.5C and discharged to the discharge cut-off voltage at the current density of 1C; 0.5C/2C represents the initial discharge specific capacity when charged to the charge cut-off voltage at a current density of 0.5C and discharged to the discharge cut-off voltage at a current density of 2C.
TABLE 1
Figure BDA0001953187430000161
Figure BDA0001953187430000171
As can be seen from Table 1, in each of examples 1 to 16, lithium praseodymium oxide is distributed on the surface of the matrix material and among primary particles of the matrix material, so that the prepared material has excellent cycle performance, the 50-week capacity retention rate is more than or equal to 91.6% under the condition of 0.5C/1C, the comprehensive electrochemical performance of example 1 is the best, and the 50-week capacity retention rate is more than 96% under the condition of 0.5C/1C.
As can be seen from Table 1, in example 4, the specific first discharge capacities under the conditions of 0.1C/0.1C, 0.5C/0.5C, 0.5C/1C and 0.5C/2C were lower than those of example 1, probably because of the Pr added in example 4 2 O 3 The content is too high, so that the active capacity of electrochemical reaction is low, and the first discharge specific capacity of the prepared material is low.
As can be seen from Table 1, the capacity retention rate at 50 weeks is lower in example 5 than in example 1 under the condition of 0.5C/1C, probably because Pr in example 5 2 O 3 The content is too low, and the content of the praseodymium lithium generated by the reaction is too low, so that the isolation between the positive active material and the electrolyte is poor, the cycle performance of the material is poor, and the capacity retention rate is low.
As can be seen from Table 1, in example 11, the specific first discharge capacities under the conditions of 0.1C/0.1C, 0.5C/0.5C, 0.5C/1C and 0.5C/2C were lower than those of example 8, probably because of free Li in example 11 + The content is too low, so that the active capacity of electrochemical reaction is low, and the first discharge specific capacity of the prepared material is low.
By passingTable 1 shows that the 50-week capacity retention is lower in example 12 compared to example 8 under 0.5C/1C, probably because of Pr in example 5 2 O 3 The content is too low, and the content of the lithium praseodymium generated by the reaction is too low, so that the isolation between the positive active material and the electrolyte is poor, side reactions and metal ions are dissolved out more, the cycle performance of the material is poor, and the capacity retention rate is low.
As can be seen from Table 1, in comparative example 1, the capacity retention ratio at 50 weeks was too low at 0.5C/1C compared to example 1, probably because Pr was not added in comparative example 1 2 O 3 On the contrary, the water washing exposes more active surfaces, which causes the side reaction to be intensified during the electrochemical reaction, and further the impedance of the anode active material is increased faster, so the cycle performance of the anode material is poor, and the specific discharge capacity is lower.
As can be seen from Table 1, comparative example 2 has a lower specific discharge capacity at 0.1C/0.1C, 0.5C/0.5C, 0.5C/1C and 0.5C/2C than example 8, and a lower capacity retention at 50 weeks at 0.5C/1C, probably because no Pr was added in comparative example 2 2 O 3 The side reactions are more during the electrochemical reaction, and the impedance of the positive active material is increased faster, so the cycle performance of the positive material is poor, and the specific discharge capacity is lower.
As can be seen from Table 1, in comparative example 3, compared with examples 1 and 8, the first discharge specific capacity is lower under the conditions of 0.1C/0.1C, 0.5C/0.5C, 0.5C/1C and 0.5C/2C, and the 50-cycle capacity retention is lower under the condition of 0.5C/1C, probably because praseodymium element exists in the form of element doping in the positive electrode material Li in comparative example 3 1.02 Ni 0.75 Co 0.1 Mn 0.1 Pr 0.05 O 2 In the method, the occurrence of side reactions on the surface of the positive electrode cannot be reduced, and meanwhile, praseodymium element cannot play a role in improving the capacity, so that the comparative example 3 has poor cycle performance and lower specific discharge capacity compared with the examples 1 and 8.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (37)

1. A positive electrode material, characterized in that the positive electrode material comprises a base material and lithium praseodymium oxide distributed on the surface of the base material and among primary particles of the base material;
the chemical general formula of the matrix material is Li z Ni 1-x-y Co x M y O 2 X is more than or equal to 0 and less than or equal to 0.35,0 and less than or equal to 0.6,0.95 and less than or equal to 1.30, M is any one or combination of at least two of Mn, al, V, mg, mo, nb and Ti;
the ratio of the molar weight of praseodymium element in the praseodymium lithium to the total molar weight of Ni element, co element and M element in the base material is 0.05-2.00 percent to 1.
2. The positive electrode material according to claim 1, wherein the chemical formula of the lithium praseodymium oxide is Li a PrO b ，2≤2b-a≤4。
3. A method for producing the positive electrode material according to claim 1 or 2, characterized by comprising the steps of:
(1) Washing the first electrode material with water, and performing solid-liquid separation to obtain a solid-phase washing product;
(2) Mixing the water washing product with a praseodymium source, and drying to obtain a pre-product;
(3) And carrying out heat treatment on the pre-product in a heat treatment atmosphere to obtain the anode material.
4. The method of claim 3, wherein the free Li of the first electrode material of step (1) + The content is 0.2-2 wt%.
5. The production method according to claim 3, wherein the first electrode material includes any one of or a combination of at least two of a Ni element, a Co element, and an M element that is any one of or a combination of at least two of a Mn element, an Al element, a V element, a Mg element, a Mo element, a Nb element, and a Ti element.
6. The method according to claim 3, wherein the temperature of the water washing is 10 to 40 ℃.
7. The method according to claim 3, wherein the washing time is 5 to 50min.
8. The method according to claim 3, wherein the mass ratio of the first electrode material to water in the water washing process is 0.5 to 4:1.
9. The method of claim 3, wherein the water content of the water-washed product is 5 to 15wt%.
10. The method according to claim 3, wherein the washing product of step (2) contains free Li + The molar ratio of the praseodymium source to the praseodymium element is 1.0-8.0.
11. The method according to claim 3, wherein the washing product and the praseodymium source are mixed by ball milling or stirring.
12. The method of claim 3, wherein the praseodymium source comprises any one of praseodymium oxide, praseodymium nitrate, and praseodymium carbonate or a combination of at least two thereof.
13. The method according to claim 3, wherein the drying temperature is 60 to 90 ℃.
14. The method according to claim 3, wherein the drying time is 0.5 to 5 hours.
15. The method according to claim 3, wherein the temperature of the heat treatment in the step (3) is 500 to 700 ℃.
16. The method according to claim 3, wherein the heat treatment is carried out for a period of 5 to 15 hours.
17. The method according to claim 3, wherein the heat treatment atmosphere comprises an oxygen atmosphere or a decarbonated air atmosphere.
18. The method for preparing a positive electrode material according to claim 3, comprising the steps of:
(1) According to the mass ratio of the first electrode material to the water of 0.5-4:1, dissociating Li + Washing the first electrode material with the content of 0.2-2 wt% for 5-50 min at the temperature of 10-40 ℃, and performing solid-liquid separation to obtain a solid-phase washing product with the water content of 5-15 wt%;
(2) Ball-milling and mixing the water washing product with a praseodymium source, wherein free Li is contained in the water washing product + The molar ratio of the precursor to praseodymium element in a praseodymium source is 1.0-8.0, and the precursor is dried at the temperature of 60-90 ℃ for 0.5-5 h to obtain a pre-product;
(3) And carrying out heat treatment on the pre-product for 5-15 h at 500-700 ℃ in an oxygen atmosphere to obtain the anode material.
19. A method for producing a positive electrode material according to claim 1 or 2, comprising the steps of:
(1) Dissolving a praseodymium source and a lithium source in water to prepare a mixed solution;
(2) Adding the mixed solution into a second electrode material to obtain an electrode material mixed solution, and drying to obtain a pre-product;
(3) And carrying out heat treatment on the pre-product in a heat treatment atmosphere to obtain the anode material.
20. The method of claim 19, wherein the free Li of the second electrode material of step (2) + The content is less than 0.2wt%.
21. The method according to claim 19, wherein the molar ratio of the lithium element in the lithium source to the praseodymium element in the praseodymium source in step (1) is 1.0 to 8.0.
22. The method of claim 19, wherein the mass ratio of the total mass of the praseodymium source and the lithium source to the water is 0.1 to 5:1.
23. The method of claim 19, wherein the praseodymium source comprises any one of praseodymium oxide, praseodymium nitrate, and praseodymium carbonate or a combination of at least two thereof.
24. The method of claim 19, wherein the lithium source comprises any one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, and lithium oxalate, or a combination of at least two thereof.
25. The production method according to claim 19, wherein the second electrode material includes any one of or a combination of at least two of a Ni element, a Co element, and an M element, which is any one of or a combination of at least two of an Mn element, an Al element, a V element, an Mg element, a Mo element, an Nb element, and a Ti element.
26. The method of claim 19, wherein the ratio of praseodymium element in the mixture of the electrode materials in step (2) to the total molar amount of the Ni element, co element and M element in the second electrode material is 0.05-2% to 1.
27. The method according to claim 19, wherein the mass ratio of the mixed solution to the second electrode material in the step (2) is 0.05 to 0.15.
28. The method of claim 19, wherein the drying temperature is 60 to 90 ℃.
29. The method of claim 19, wherein the drying time is 0.5 to 5 hours.
30. The method according to claim 19, wherein the temperature of the heat treatment in the step (3) is 500 to 700 ℃.
31. The method of claim 19, wherein the heat treatment time is 5 to 15 hours.
32. The method of claim 19, wherein the heat treatment atmosphere comprises an oxygen atmosphere or a decarbonated air atmosphere.
33. The method for preparing a positive electrode material according to claim 19, comprising the steps of:
(1) Dissolving a praseodymium source and a lithium source in water according to the molar ratio of the lithium element in the lithium source to the praseodymium element in the praseodymium source of 1.0-8.0 to prepare a mixed solution;
(2) According to the mass ratio of the mixed liquid to the second electrode material of 0.05-0.15 + Adding a second electrode material with the content of less than 0.2wt% into the mixed solution, and drying at the temperature of between 60 and 90 ℃ for 0.5 to 5 hours to obtain a pre-product;
(3) And carrying out heat treatment on the pre-product for 5-15 h at 500-700 ℃ in an oxygen atmosphere to obtain the anode material.
34. Use of the positive electrode material according to claim 1 or 2, wherein the positive electrode material is used in the field of batteries.
35. Use of the positive electrode material according to claim 34, wherein the positive electrode material is used in the field of positive electrode materials for lithium ion batteries.
36. A lithium ion battery comprising the positive electrode material according to claim 1 or 2.
37. The lithium ion battery according to claim 36, wherein the positive electrode material of the lithium ion battery is the positive electrode material according to claim 1 or 2.
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