CN111430680B - Modified quaternary positive electrode material and preparation method and application thereof - Google Patents
Modified quaternary positive electrode material and preparation method and application thereof Download PDFInfo
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- CN111430680B CN111430680B CN201911198062.7A CN201911198062A CN111430680B CN 111430680 B CN111430680 B CN 111430680B CN 201911198062 A CN201911198062 A CN 201911198062A CN 111430680 B CN111430680 B CN 111430680B
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- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000011247 coating layer Substances 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010405 anode material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 11
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- 239000010410 layer Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
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- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 238000005253 cladding Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 44
- 238000001354 calcination Methods 0.000 claims description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
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- 239000004327 boric acid Substances 0.000 claims description 4
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- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 4
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- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 2
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- 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
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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
- 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
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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
- H01M4/36—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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- 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
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Abstract
The invention discloses a modified quaternary anode material for a lithium battery, a preparation method thereof and the lithium battery with the modified quaternary anode material. The modified quaternary positive electrode material comprises: a quaternary positive electrode material core; a first cladding layer comprising Li2O‑2B2O3(lithium tetraborate) with the first coating layer formed on at least a portion of the surface of the quaternary positive electrode material core; a second coating layer containing an oxide and/or hydroxide of M, M being at least one of Mg, Al, Zr, Ti, Fe, formed on at least a part of a surface of the first coating layer. The modified quaternary positive electrode material adopts Li2O‑2B2O3The conductive glass and the metal oxide and/or hydroxide are subjected to secondary coating modification, so that excellent capacity, first effect and cycle performance can be obtained.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a modified quaternary anode material for a lithium battery, a preparation method of the modified quaternary anode material and the lithium battery with the modified quaternary anode material.
Background
Currently, the automotive industry is faced with increasingly stringent requirements in terms of fuel economy and emissions reduction. Therefore, much attention has been paid to rechargeable lithium ion batteries used in electric and electric hybrid vehicles. In lithium ion batteries, the positive electrode material plays a crucial role. At present, nickel-rich lithium transition metal oxides are considered as the most promising candidate materials because they can increase the specific capacity of lithium ion batteries by increasing the nickel content. However, the poor cycling stability and rate capability of the resulting lithium ion batteries may hinder the use of such materials.
Therefore, the existing quaternary positive electrode materials still need to be studied intensively.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a modified quaternary cathode material, a preparation method and application thereof. The modified quaternary positive electrode material adopts Li2O-2B2O3Conductive glass and metal oxideThe compound and/or the hydroxide are subjected to secondary coating modification, so that excellent capacity, first effect and cycle performance can be obtained.
In one aspect of the invention, a modified quaternary positive electrode material for a lithium battery is provided. According to an embodiment of the present invention, the modified quaternary positive electrode material includes: a quaternary positive electrode material core; a first cladding layer comprising Li2O-2B2O3The first coating layer is formed on at least part of the surface of the quaternary positive electrode material core; a second coating layer containing an oxide and/or hydroxide of M, M being at least one of Mg, Al, Zr, Ti, Fe, formed on at least a part of a surface of the first coating layer.
A modified quaternary positive electrode material according to an embodiment of the present invention has a positive electrode material including Li2O-2B2O3A first coating layer of (lithium tetraborate, LBO) conductive glass and a second coating layer comprising a metal (M) oxide and/or hydroxide. LBO is a conductor with good lithium ion conductivity, has good wetting property and relatively low viscosity, is easy to form a uniform coating on the surface of the quaternary positive electrode material core and coat the quaternary positive electrode material core body, and improves the process of lithium ion extraction and insertion in the positive electrode material. On the other hand, the second coating layer can play a better supporting role because the cathode material coated by the M element is stable under a high oxidation potential. Under the high-voltage charging state, a large amount of lithium ions are intercalated, M can effectively maintain the stability of a lattice structure in the form of ions, the transformation from a layered structure to a spinel structure and the mixed discharge of lithium ions/nickel ions are inhibited, and more reversible lithium sites are reserved, so that the reversible discharge capacity of the material is improved, and the first-effect performance of the battery is improved. In addition, the bonding force among M(s) -O (p) bonds in the material is far greater than that of Ni-O bonds, Co-O bonds or Mn-O bonds, so that the coating of the M element can effectively inhibit the positive electrode material from seriously releasing oxygen, unstable lattice structure, easy structural collapse and phase change and the like under high cut-off voltage, thereby improving the high-current charge and discharge performance and long-cycle stability of the battery. In summary, the present inventionThe modified quaternary positive electrode material has excellent capacity, first effect and cycle performance.
In addition, the modified quaternary positive electrode material according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the quaternary positive electrode material core has a composition as shown in formula (I),
LiNixCoyMnzAl(1-x-y-z)O2 (I)
in the formula (I), x is more than or equal to 0.8 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.1, and z is more than or equal to 0 and less than or equal to 0.1.
In some embodiments of the present invention, the mass of the first coating layer is 0.0005 to 1% of the total mass of the modified quaternary positive electrode material.
In some embodiments of the present invention, the mass of the second coating layer is 0.0005 to 1% of the total mass of the modified quaternary positive electrode material.
In another aspect of the present invention, the present invention provides a method of preparing the modified quaternary positive electrode material of the above embodiment. According to an embodiment of the invention, the method comprises: (1) mixing a lithium source, a boron source and a solvent to obtain a coating solution; (2) mixing the coating solution with a quaternary anode material precursor to obtain a first mixed material; (3) carrying out first calcination treatment on the first mixed material to obtain a first product; (4) mixing the first product with an M source to obtain a second mixed material; (5) and carrying out second calcination treatment on the second mixed material to obtain the modified quaternary anode material. Therefore, the method forms the first coating layer through wet coating and forms the second coating layer through dry coating, so that the high-performance modified quaternary positive electrode material is prepared, and the method is simple to operate, short in period and easy to implement industrially.
In addition, the method for preparing the modified quaternary positive electrode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the lithium source comprises at least one selected from the group consisting of lithium nitrate, lithium carbonate, lithium hydroxide monohydrate.
In some embodiments of the present invention, the boron source comprises at least one selected from boric acid, boron oxide.
In some embodiments of the invention, the first calcination treatment is performed at 600-1050 ℃ for 5-15 h.
In some embodiments of the invention, the first mix is previously subjected to a heat treatment to remove the solvent before the first calcination treatment.
In some embodiments of the present invention, the second calcination treatment is performed at 200 to 650 ℃ for 5 to 10 hours.
In yet another aspect of the present invention, a lithium ion battery is presented. According to an embodiment of the present invention, the lithium ion battery includes: the modified quaternary positive electrode material of the above embodiment. Therefore, the lithium ion battery has all the characteristics and advantages described above for the modified quaternary positive electrode material, and the description thereof is omitted. In general, the lithium ion battery has excellent electric properties such as capacity, first effect and cycle performance.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow chart of a method for preparing a modified quaternary positive electrode material according to an embodiment of the present invention;
FIG. 2 is a first charge-discharge curve diagram of modified quaternary cathode material product A prepared in example 1;
fig. 3 is a first charge-discharge curve diagram of the modified quaternary positive electrode material product B prepared in comparative example 1;
fig. 4 is a graph of cycle capacity retention for modified quaternary positive electrode material products a and B.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a modified quaternary positive electrode material for a lithium battery is provided. According to an embodiment of the present invention, the modified quaternary positive electrode material includes: a quaternary positive electrode material core; a first cladding layer comprising Li2O-2B2O3The first coating layer is formed on at least part of the surface of the quaternary positive electrode material core; a second coating layer containing an oxide and/or hydroxide of M, M being at least one of Mg, Al, Zr, Ti, Fe, formed on at least a part of a surface of the first coating layer.
In research, the inventor finds that LBO is a conductor with good lithium ion conductivity, has good wetting property and relatively low viscosity, is easy to form a uniform coating on the surface of the quaternary positive electrode material core and coat the quaternary positive electrode material core body, and improves the process of lithium ion extraction and insertion in the positive electrode material. In a high-voltage lithium ion battery, excessive lithium ion extraction may improve the charging specific capacity of the battery, but the internal collapse of the material or the mixed discharge of lithium ions and nickel ions is likely to occur, which may cause adverse effects on the first-effect performance and long-cycle performance of the battery. According to the modified quaternary positive electrode material provided by the invention, the second coating layer containing metal oxide and/or hydroxide is further formed outside the LBO first coating layer, and the second coating layer can play a better supporting role because the positive electrode material coated by the M element is stable under a high oxidation potential. Under the high-voltage charging state, a large amount of lithium ions are intercalated, M can effectively maintain the stability of a lattice structure in the form of ions, the transformation from a layered structure to a spinel structure and the mixed discharge of lithium ions/nickel ions are inhibited, and more reversible lithium sites are reserved, so that the reversible discharge capacity of the material is improved, and the first-effect performance of the battery is improved. In addition, the bonding force among M(s) -O (p) bonds in the material is far greater than that of Ni-O bonds, Co-O bonds or Mn-O bonds, so that the coating of the M element can effectively inhibit the positive electrode material from seriously releasing oxygen, unstable lattice structure, easy structural collapse and phase change and the like under high cut-off voltage, thereby improving the high-current charge and discharge performance and long-cycle stability of the battery. In conclusion, the modified quaternary positive electrode material provided by the invention has excellent capacity, first effect and cycle performance.
The modified quaternary positive electrode material according to an embodiment of the present invention is further described in detail below.
According to some embodiments of the present invention, the quaternary positive electrode material core may be a nickel-cobalt-manganese-aluminum quaternary positive electrode material (NCMA material) commonly used in the art. The technical scheme of the invention can obviously improve the capacity, the first effect and the cycle performance of the NCMA material by carrying out dry-wet secondary coating modification on the existing NCMA material. In some embodiments, the quaternary positive electrode material core has a composition as shown in formula (I),
LiNixCoyMnzAl(1-x-y-z)O2 (I)
in the formula (I), x is more than or equal to 0.8 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.1, and z is more than or equal to 0 and less than or equal to 0.1.
According to some embodiments of the present invention, the mass of the first coating layer accounts for 0.0005 to 1% of the total mass of the modified quaternary positive electrode material, for example, 0.0005%, 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, and the like. By controlling the quality of the first coating layer within the range, the LBO content in the modified quaternary positive electrode material is proper, and the overall lithium removal/insertion performance of the modified quaternary positive electrode material can be further improved. If the content of LBO in the modified quaternary positive electrode material is too high, the coating layer is too thick, the conductivity of the material is poor, and lithium ions are difficult to be extracted and inserted, so that the electrochemical performance of the material is influenced.
According to some embodiments of the present invention, the mass of the second coating layer accounts for 0.0005 to 1% of the total mass of the modified quaternary positive electrode material, for example, 0.0005%, 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, and the like. By controlling the quality of the second coating layer within the range, the content of M oxide or M hydroxide in the modified quaternary positive electrode material is appropriate, and the overall stability of the modified quaternary positive electrode material can be further improved. If the content of the M oxide or the M hydroxide in the modified quaternary positive electrode material is too high, the coating layer is too thick or the coating is not uniform, the conductivity of the material is poor, and lithium ions are difficult to be extracted and inserted, so that the electrochemical performance of the material is affected.
In another aspect of the present invention, the present invention provides a method of preparing the modified quaternary positive electrode material of the above embodiment. According to an embodiment of the invention, the method comprises: (1) mixing a lithium source, a boron source and a solvent to obtain a coating solution; (2) mixing the coating solution with a quaternary anode material precursor to obtain a first mixed material; (3) carrying out first calcination treatment on the first mixed material to obtain a first product; (4) mixing the first product with an M source to obtain a second mixed material; (5) and carrying out second calcination treatment on the second mixed material to obtain the modified quaternary anode material. Therefore, the method forms the first coating layer through wet coating and forms the second coating layer through dry coating, so that the high-performance modified quaternary positive electrode material is prepared, and the method is simple to operate, short in period and easy to implement industrially.
The method for preparing the modified quaternary positive electrode material according to the embodiment of the present invention is further described in detail below. Referring to fig. 1, according to an embodiment of the invention, the method comprises:
s100: obtaining a coating solution
In this step, a lithium source, a boron source, and a solvent are mixed to obtain a coating liquid. Specifically, after mixing the lithium source, the boron source and the solvent, strong stirring can be assisted to ensure that the mixture is straightUntil the components are completely dissolved, wherein the lithium source and the boron source are mixed according to the molar ratio of the lithium element to the boron element of 1:2 so as to obtain Li2O-2B2O3Conductive glass. The specific kind of the solvent is not particularly limited as long as the lithium source and the boron source can be well dispersed, and in some embodiments of the present invention, ethanol is used as the solvent.
According to some embodiments of the present invention, the lithium source may include at least one selected from the group consisting of lithium nitrate, lithium carbonate, and lithium hydroxide monohydrate, preferably lithium hydroxide monohydrate.
According to some embodiments of the present invention, the boron source may comprise at least one selected from boric acid, boron oxide, preferably boric acid.
S200: wet coating
In the step, the coating solution is mixed with a quaternary anode material precursor to obtain a first mixed material. According to some embodiments of the present invention, the mixing ratio of the coating solution and the quaternary positive electrode material precursor may be: the ratio of the molar quantity of the lithium element in the coating liquid to the total molar quantity of the metal elements in the quaternary anode material precursor is 1 (1.01-1.03), and preferably 1: 1.025.
S300: first calcination treatment
In this step, the first mixed material is subjected to a first calcination treatment in an oxidizing atmosphere (e.g., an oxygen atmosphere) to obtain a quaternary positive electrode material core and a stable LBO coating layer.
According to some embodiments of the present invention, the first calcination treatment may be performed at 600 to 1050 ℃ for 5 to 15 hours. Specifically, the calcination temperature may be 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1050 ℃ and the like, and the calcination time may be 5 hours, 7.5 hours, 10 hours, 12.5 hours, 15 hours and the like. The inventor finds that if the temperature of the first calcination process is too low or the time is too short, the reaction may be incomplete, an amorphous material is easily generated, the crystallization performance of the material is not good, and the material is easy to contain impurity phases, and the electrochemical performance of the material is greatly influenced; if the temperature of the first calcination process is too high or the time is too long, oxygen-deficient compounds may be generated and secondary recrystallization may be promoted, and the material has large crystal grains and small specific surface area, which is not favorable for lithium ion extraction and intercalation in the material.
According to some embodiments of the present invention, the first mixed material may be previously subjected to a heat treatment to remove the solvent therefrom before the first calcination treatment is performed. In particular, the first batch may be heated slightly at a temperature slightly above the boiling point of the solvent used until the solvent in the batch is completely volatilized. According to some embodiments of the present invention, when ethanol is used as the solvent, the temperature of the heat treatment may be 60 ℃.
According to some embodiments of the present invention, after the first calcination treatment, the resulting first product may be cooled, pulverized and sieved. The target particle size for crushing the first product is not particularly limited and may be selected according to actual needs.
S400: dry coating
In this step, the first product is mixed with an M source to obtain a second mixture. Specifically, M may be at least one of Mg, Al, Zr, Ti, and Fe. The source of M may be an oxide and/or hydroxide of M.
S500: second calcination treatment
In this step, the second mixed material is subjected to a second calcination treatment in an oxidizing atmosphere (e.g., an oxygen atmosphere) to form a stable second coating layer outside the first coating layer, resulting in a modified quaternary positive electrode material.
According to some embodiments of the present invention, the second calcination treatment may be performed at 200 to 650 ℃ for 5 to 10 hours. Specifically, the calcination temperature may be 200 ℃, 300 ℃, 400 ℃, 500 ℃, 650 ℃ and the like, and the calcination time may be 5 hours, 6 hours, 7 hours, 8 hours, 10 hours and the like. The inventors found that if the temperature of the second calcination treatment is too low or the treatment time is too short, the coating on the surface of the positive electrode material may not be uniform, and if the temperature of the second calcination treatment is too high or the treatment time is too long, aluminum ions may enter the inside of the positive electrode material body and may not play a role in the required coating.
According to some embodiments of the present invention, after the second calcination treatment, the resulting modified quaternary positive-electrode material product may be cooled, pulverized, and sieved. The target particle size for crushing the modified quaternary positive electrode material product is not particularly limited and can be selected according to actual needs.
In yet another aspect of the present invention, a lithium ion battery is presented. According to an embodiment of the present invention, the lithium ion battery includes: the modified quaternary positive electrode material of the above embodiment. Therefore, the lithium ion battery has all the characteristics and advantages described above for the modified quaternary positive electrode material, and the description thereof is omitted. In general, the lithium ion battery has excellent electric properties such as capacity, first effect and cycle performance.
According to some embodiments of the invention, the lithium battery comprises: a positive electrode, a negative electrode, a separator and an electrolyte; wherein, positive pole includes: the positive pole current collector and the positive pole material of load on the positive pole current collector, positive pole material includes: a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; the positive electrode active material is the modified quaternary positive electrode material of the embodiment. The negative electrode includes: the negative electrode comprises a negative electrode current collector and a negative electrode material loaded on the negative electrode current collector, wherein the negative electrode material comprises: a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
According to some embodiments of the present invention, the positive electrode material includes a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder; the mass ratio of the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is not particularly limited, and may be selected according to actual needs. The positive electrode active material is the modified quaternary positive electrode material of the above embodiment. The specific types of the positive electrode conductive agent and the positive electrode binder are not particularly limited, and for example, the positive electrode conductive agent may be at least one of common positive electrode binders such as conductive carbon black SP or ECP, carbon nanotubes (CNT or WCNT), graphene, and the like; the positive electrode binder may be at least one of common positive electrode binders such as polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), and the like. The positive electrode material may further include a common solvent (e.g., NMP) for mixing the positive electrode material, and the ratio of the solvent to the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is not particularly limited, and may be selected by those skilled in the art according to actual needs.
According to some embodiments of the present invention, the negative electrode material includes a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder; the mass ratio of the negative electrode active material, the negative electrode conductive agent, the negative electrode binder, and the thickening stabilizer is not particularly limited, and may be selected according to actual needs. The specific types of the negative electrode active material, the negative electrode conductive agent and the negative electrode binder are not particularly limited, and the negative electrode active material can be at least one of common negative electrode active materials selected from natural graphite, artificial graphite, mesophase microspheres, soft carbon, hard carbon and the like; the negative electrode conductive agent can be at least one of conductive carbon black SP or ECP, carbon nano tube (CNT or WCNT), graphene and other common negative electrode conductive agents; the negative electrode binder may be at least one of common negative electrode binders such as polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), and the like. In addition, the negative electrode material may further include a common solvent (e.g., NMP, deionized water, etc.) for mixing the negative electrode material, and the solvent is not particularly limited and may be selected by those skilled in the art according to actual needs.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) Reacting LiOH & H2O and H3BO3Dissolving the materials in ethanol according to the molar ratio of 1:2, and stirring until the components are completely dissolved to obtain the LBO conductive glass. Adding nickel cobalt manganese aluminum hydroxide (molar ratio: Ni: Co: Mn: Al: 88:6:3:3) powder into the LBO coating solution, wherein the mixing ratio is as follows: the ratio of the molar quantity of the lithium element in the coating liquid to the total molar quantity of the metal elements in the quaternary anode material precursor is 1: 1.025. Slightly heating the mixed solution to 60 ℃, after the solvent is completely evaporated, filling the powder into a crucible, and calcining for 10 hours at 800 ℃ in an oxygen atmosphere to obtain a first product.
(2) Reacting the first product with Al (OH)3Dry mixing according to the mass ratio of 100:0.05, calcining at 400 ℃ in an oxygen atmosphere after uniform mixingAnd (5) burning for 6 hours. And cooling, crushing and sieving to obtain a modified quaternary anode material product A with the target granularity.
Comparative example 1
Reacting LiOH & H2O and H3BO3Dissolving the materials in ethanol according to the molar ratio of 1:2, and stirring until the components are completely dissolved to obtain the LBO conductive glass. Adding nickel cobalt manganese aluminum hydroxide (molar ratio: Ni: Co: Mn: Al: 88:6:3:3) powder into the LBO coating solution, wherein the mixing ratio is as follows: the ratio of the molar quantity of the lithium element in the coating liquid to the total molar quantity of the metal elements in the quaternary anode material precursor is 1: 1.025. Slightly heating the mixed solution to 60 ℃, after the solvent is completely evaporated, filling the powder into a crucible, and calcining for 10 hours at 800 ℃ in an oxygen atmosphere to obtain a modified quaternary positive material product B.
Example 3
The modified quaternary positive electrode material products a and B prepared in the above example 1 and comparative example 1 were respectively taken, and the positive electrode material, the carbon black conductive agent, the binder PVDF and NMP in a mass ratio of 95:2.5:2.5:5 were uniformly mixed to prepare the battery positive electrode slurry. Coating the slurry on an aluminum foil with the thickness of 20-40 mu M, and preparing a positive electrode plate by vacuum drying and rolling, wherein a lithium metal plate is used as a negative electrode, and the electrolyte ratio is 1.15M LiPF6And assembling the button cell with the volume ratio of ethylene carbonate to diethyl carbonate being 1:1.
The electrical property test of the material is respectively carried out by adopting a blue battery test system at 25 ℃, the test voltage range is 3-4.5V, and the cycle capacity retention rate of 50 circles is tested, and the test result is shown in table 1.
Through test analysis, the first charge-discharge curve of the modified quaternary positive electrode material product a in example 1 is shown in fig. 2, the first charge-discharge curve of the modified quaternary positive electrode material product B in comparative example 1 is shown in fig. 3, and the cycle capacity retention ratio curves of the modified quaternary positive electrode material products a and B are shown in fig. 4. The comparison result shows that the modified quaternary anode material prepared by the method provided by the embodiment of the invention has higher capacity, first effect and cycle capacity retention rate.
TABLE 1 test results
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. A modified quaternary positive electrode material for a lithium battery, comprising:
a quaternary positive electrode material core;
a first cladding layer comprising Li2O-2B2O3The first coating layer is formed on at least part of the surface of the quaternary positive electrode material core;
a second clad layer containing an oxide and/or hydroxide of M, M being at least one of Mg, Al, Zr, Ti, Fe, the second clad layer being formed on at least a part of a surface of the first clad layer,
wherein,
the mass of the first coating layer accounts for 0.0005-1% of the total mass of the modified quaternary positive electrode material;
the second coating layer accounts for 0.0005-1% of the total mass of the modified quaternary positive electrode material.
2. The modified quaternary positive electrode material of claim 1, wherein the quaternary positive electrode material core has a composition as shown in formula (I),
LiNixCoyMnzAl(1-x-y-z)O2 (I)
in the formula (I), x is more than or equal to 0.8 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.1, and z is more than or equal to 0 and less than or equal to 0.1.
3. A method of preparing the modified quaternary positive electrode material of claim 1 or 2, comprising:
(1) mixing a lithium source, a boron source and a solvent to obtain a coating solution;
(2) mixing the coating solution with a quaternary anode material precursor to obtain a first mixed material;
(3) carrying out first calcination treatment on the first mixed material to obtain a first product;
(4) mixing the first product with an M source to obtain a second mixed material;
(5) and carrying out second calcination treatment on the second mixed material to obtain the modified quaternary anode material.
4. The method of claim 3, wherein the lithium source comprises at least one selected from the group consisting of lithium nitrate, lithium carbonate, and lithium hydroxide monohydrate.
5. The method of claim 3, wherein the boron source comprises at least one selected from boric acid and boron oxide.
6. The method according to claim 3, wherein the first calcination treatment is performed at 600 to 1050 ℃ for 5 to 15 hours.
7. A method according to claim 3, characterized in that, before the first calcination treatment, the first mix is subjected to a heat treatment beforehand in order to remove the solvent.
8. The method according to claim 3, wherein the second calcination treatment is performed at 200 to 650 ℃ for 5 to 10 hours.
9. A lithium ion battery, comprising: the modified quaternary positive electrode material of claim 1 or 2.
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| CN109643794A (en) * | 2017-02-02 | 2019-04-16 | 株式会社Lg化学 | Cathode active material for secondary battery and preparation method thereof |
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| CN109473657A (en) * | 2018-12-03 | 2019-03-15 | 林奈（中国）新能源有限公司 | A kind of nickel cobalt aluminium manganese quaternary lithium-ion battery positive electrode material being mixed with, Preparation method and use |
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