CN117996055A - Ternary positive electrode material, preparation method thereof, lithium ion battery and electronic equipment - Google Patents
Ternary positive electrode material, preparation method thereof, lithium ion battery and electronic equipment Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 67
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 40
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- 239000000843 powder Substances 0.000 claims description 29
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 28
- 239000010406 cathode material Substances 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 19
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 19
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 18
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 18
- 239000011247 coating layer Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
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- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
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- 239000002245 particle Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
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- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 7
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- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 claims description 5
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
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- 229910013641 LiNbO 3 Inorganic materials 0.000 description 12
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- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
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- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a ternary positive electrode material, a preparation method thereof, a positive electrode plate, a lithium ion battery and electronic equipment. The ternary positive electrode material provided by the application can improve the cycle stability and the conductivity of the lithium ion battery.
Description
Technical Field
The application relates to the technical field of electrochemistry, in particular to a ternary positive electrode material, a preparation method thereof, a lithium ion battery and electronic equipment.
Background
The secondary battery represented by the lithium ion battery has the advantages of high working voltage, high energy density, good safety, no memory effect and the like, and has been greatly successful in the fields of portable electronic equipment, electric automobiles, hybrid electric automobiles and the like. At present, in the traditional lithium ion battery, ternary materials such as lithium, nickel, cobalt, manganese and the like are widely applied to a positive electrode material due to the advantages of higher capacity, energy density and the like, but the battery containing the ternary positive electrode material such as lithium, nickel, cobalt, manganese and the like is generally poor in cycling stability under high voltage.
Disclosure of Invention
Based on the above, the application provides a ternary positive electrode material, a preparation method thereof, a positive electrode plate, a lithium ion battery and electronic equipment, and the cycling stability of the lithium ion battery at high voltage can be improved.
According to a first aspect of the application, a ternary positive electrode material is provided, which comprises lithium nickel cobalt manganese oxide and a coating layer coated on at least part of the surface of the lithium nickel cobalt manganese oxide, wherein the bulk phase of the lithium nickel cobalt manganese oxide contains niobium element and zirconium element, and the coating layer contains lithium phosphate and polypyrrole.
In some embodiments of the present application, at least one of the following conditions is satisfied:
(1) The total content of the niobium element and the zirconium element in the ternary positive electrode material is 70000 ppm-9000 ppm;
(2) The total content of the lithium phosphate and the polypyrrole in the ternary positive electrode material is 4000 ppm-6000 ppm;
(3) The thickness of the coating layer is 15 nm-20 nm.
In some embodiments of the application, the shallow surface layer of lithium nickel cobalt manganese oxide comprises magnesium element;
Optionally, the content of the magnesium element in the ternary positive electrode material is 1500 ppm-3000 ppm.
In some embodiments of the present application, at least one of the following conditions is satisfied:
(1) The bulk phase of the lithium nickel cobalt manganese oxide contains ionic bonds formed by niobium element and zirconium element respectively and respectively with oxygen element;
(2) The bulk phase of the lithium nickel cobalt manganese oxide comprises Nb 5+ and Zr 4+;
(3) The lithium nickel cobalt manganese oxide satisfies the chemical formula Li αNiaCobMn（1-a-b）NbcZrdO2, wherein alpha is more than or equal to 1.05 and less than or equal to 1.12,0.93 and a is more than or equal to 0.95,0.02 and less than or equal to 0.04,0.1, c is more than or equal to 0.2,0.2 and d is more than or equal to 0.4;
(4) The particle size D50 of the ternary positive electrode material meets the following conditions: d50 is more than or equal to 9.5 mu m and less than or equal to 11.5 mu m.
A second aspect of the present application provides a method of preparing a ternary cathode material, comprising:
Performing first sintering treatment on a first mixture containing a ternary precursor, a lithium source and a bimetallic oxide cluster powder containing lithium niobate and lithium zirconate to prepare a lithium nickel cobalt manganese oxide, wherein the bulk phase of the lithium nickel cobalt manganese oxide contains niobium element and zirconium element;
And performing second sintering treatment on the second mixture containing the lithium nickel cobalt manganese oxide, magnesium hydrogen phosphate and polypyrrole, and forming a coating layer containing lithium phosphate and the polypyrrole on at least part of the surface of the lithium nickel cobalt manganese oxide to prepare the ternary positive electrode material.
In some embodiments of the present application, at least one of the following conditions is satisfied:
(1) The particle diameter D50 of the bimetallic oxide cluster powder containing lithium niobate and lithium zirconate is below 0.1 mu m;
(2) In the bimetallic oxide cluster powder containing lithium niobate and lithium zirconate, the molar ratio of the lithium niobate to the lithium zirconate is 1 (1.6-2.0);
(3) The particle size D50 of the lithium nickel cobalt manganese oxide is 9.2-11 mu m;
(4) The temperature of the first sintering treatment is 750-850 ℃;
(5) The time of the first sintering treatment is 10-15 h.
In some embodiments of the present application, at least one of the following conditions is satisfied:
(1) In the second mixture, the mass ratio of the magnesium hydrophosphate to the polypyrrole is 1 (1-1.5);
(2) The temperature of the second sintering treatment is 300-380 ℃;
(3) The time of the second sintering treatment is 12-15 h.
In some embodiments of the present application, the method for preparing the lithium niobate and lithium zirconate-containing bi-metal oxide cluster powder includes:
performing heat treatment on a mixture containing lithium niobate and lithium zirconate to prepare the bimetal oxide cluster powder containing lithium niobate and lithium zirconate;
optionally, the molar ratio of the lithium niobate to the lithium zirconate is 1 (1.6-2.0);
Optionally, the temperature of the heat treatment is 450-550 ℃;
Optionally, the heat treatment time is 8-10 h.
A third aspect of the application provides a lithium ion battery comprising a ternary cathode material according to the first aspect of the application or a ternary cathode material prepared by a method according to the second aspect of the application.
A fourth aspect of the application provides an electronic device comprising a lithium ion battery of the third aspect of the application.
The ternary positive electrode material provided by the application comprises the lithium nickel cobalt manganese oxide and the coating layer, wherein the bulk phase of the lithium nickel cobalt manganese oxide contains niobium element and zirconium element, the niobium element can regulate and control radial growth and accumulation of spherical particles of the lithium nickel cobalt manganese oxide, the structure accumulation is compact, the pulverization of the lithium nickel cobalt manganese oxide can be inhibited during continuous charge and discharge, and the cyclic stability of the material is improved. The radius of the zirconium element is larger than that of transition metal elements (such as nickel, cobalt and manganese), so that the interlayer spacing can be increased after the zirconium element enters a bulk phase lattice of the lithium nickel cobalt manganese oxide, a Li + migration channel is widened, the Li + transport dynamics is faster, and the impedance is reduced, so that the multiplying power performance and the cycling stability of the material under high voltage are improved. Meanwhile, the coating layer contains lithium phosphate and polypyrrole, the lithium phosphate is used as a fast ion conductor to accelerate the Li + transmission rate of an interface, and the lithium phosphate and the polypyrrole with high conductivity can mutually cooperate to promote the quick transmission of Li +, so that the rate capability of the ternary positive electrode material is further effectively improved.
Drawings
Fig. 1 is a scanning electron microscope image of the ternary cathode material prepared in example 1.
Fig. 2 is a hard cross-sectional view of the ternary cathode material prepared in example 1.
Detailed Description
The present application will be described more fully hereinafter in order to facilitate an understanding of the present application. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
For simplicity, only a few numerical ranges are explicitly disclosed. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. It is noted that, as used herein, unless otherwise indicated, the term "and/or" includes any and all combinations of one or more of the associated listed items, "above," below, "and" comprise the present number, and the meaning of "multiple" in "one or more" is two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In the various examples, the list is merely a representative group and should not be construed as exhaustive.
Generally, the energy density of ternary materials such as lithium, nickel, cobalt, manganese and the like gradually increases with the increase of the nickel content, but the capacity thereof is drastically reduced. The inventors have found that this is caused by mechanisms such as phase transition, microcracking, interfacial reaction side reaction, and the like occurring between the electrolyte and the nickel-rich cathode material. To reduce the capacity fade problem of nickel-rich cathode materials, surface modification and ion doping are the most effective two methods, wherein ion doping is commonly found in high temperature solid phase stages, typically by high speed mixing and sintering of different doping additives, precursors, lithium salts. However, such a mixed material directly added with different additives and sintering method are difficult to disperse them in a lithium nickel cobalt manganese layered structure according to a specific ratio, which tends to cause instability in electrochemical performance of the cathode material. Therefore, how to make the effect of the doping additive more effectively exerted and to make the output of the prepared cathode material stable and excellent in electrochemical performance becomes a difficulty of research in the art. Accordingly, the present inventors have proposed the following technical solutions.
A first aspect of the present application provides a ternary cathode material (see fig. 1 and 2) comprising a lithium nickel cobalt manganese oxide comprising niobium and zirconium elements in a bulk phase and a coating layer over at least part of the surface of the lithium nickel cobalt manganese oxide, the coating layer comprising lithium phosphate and polypyrrole.
It is understood that the term "bimetallic oxide cluster" as used herein refers to a macromolecular species formed by one or more groups of metal atoms (as the host element, such as niobium and zirconium atoms) bonded together with oxygen atoms (as the host element).
The ternary positive electrode material provided by the application comprises the lithium nickel cobalt manganese oxide and the coating layer, wherein the bulk phase of the lithium nickel cobalt manganese oxide contains niobium element and zirconium element, the niobium element can regulate and control radial growth and accumulation of spherical particles of the lithium nickel cobalt manganese oxide, the structure accumulation is compact, the pulverization of the lithium nickel cobalt manganese oxide can be inhibited during continuous charge and discharge, and the cyclic stability of the material is improved. The radius of the zirconium element is larger than that of transition metal elements (such as nickel, cobalt and manganese), so that the interlayer spacing can be increased after the zirconium element enters a bulk phase lattice of the lithium nickel cobalt manganese oxide, a Li + migration channel is widened, the Li + transport dynamics is faster, and the impedance is reduced, so that the multiplying power performance and the cycling stability of the material under high voltage are improved. Meanwhile, the coating layer contains lithium phosphate and polypyrrole, the lithium phosphate is used as a fast ion conductor to accelerate the Li + transmission rate of an interface, and the lithium phosphate and the polypyrrole with high conductivity can mutually cooperate to promote the quick transmission of Li +, so that the rate capability of the ternary positive electrode material is further effectively improved.
In some embodiments, the total content of the niobium element and the zirconium element in the ternary cathode material is 70000 ppm to 9000ppm. For example, the content may be 7000ppm,7500ppm,8000ppm,8500ppm,9000ppm or within a range composed of any of the above values.
In some embodiments, the total content of the lithium phosphate and the polypyrrole in the ternary positive electrode material is 4000ppm to 6000ppm. For example, the total content may be 4000ppm,4500ppm,5000ppm,5500ppm,6000ppm or within a range comprised of any of the above values.
In some embodiments, the thickness of the coating layer is 15 nm-20 nm. For example, the thickness of the coating layer may be 15nm,16nm,17nm,19nm,20nm or within a range consisting of any of the above values.
In some embodiments, the shallow surface layer of lithium nickel cobalt manganese oxide comprises elemental magnesium.
The term "shallow layer" as used herein refers to a region extending from any point on the surface of the lithium nickel cobalt manganese oxide to the center thereof to 0.1 μm to 0.4 μm.
The shallow surface layer of the lithium nickel cobalt manganese oxide contains magnesium element, which is favorable for further improving the stability of the layered structure of the material and reducing the performance degradation caused by excessive erosion of the electrolyte.
In some embodiments, the magnesium element is contained in the ternary positive electrode material in an amount of 1500ppm to 3000ppm. For example, the content may be 1500ppm,2000ppm,2500ppm,3000ppm or within a range comprised of any of the above values.
In some embodiments, nb 5+ and Zr 4+ are included in the bulk phase of the lithium nickel cobalt manganese oxide.
It is understood that the term "bulk phase of lithium nickel cobalt manganese oxide" as used herein refers to the lattice structure that forms the lithium nickel cobalt manganese oxide.
Nb 5+ and Zr 4+ are contained in the bulk phase of the lithium nickel cobalt manganese oxide, wherein Nb 5+ can regulate radial growth and accumulation of spherical particles of the lithium nickel cobalt manganese oxide, the structure is compact in accumulation, pulverization of the lithium nickel cobalt manganese oxide can be restrained during continuous charge and discharge, and the cyclic stability of the material is improved. And because the radius of Zr 4+ is larger than that of transition metals (such as Ni 2+,Co3+ and Mn 4+), the interlayer spacing can be increased after Zr 4+ enters the bulk phase lattice of the lithium nickel cobalt manganese oxide, the migration channel of Li + is widened, the transport kinetics of Li + is faster, and the impedance is reduced, so that the rate capability and the cycling stability of the material under high voltage are further improved.
In some embodiments, the lithium nickel cobalt manganese oxide contains ionic bonds formed by niobium element and zirconium element and oxygen element respectively.
The Nb element and the Zr element can respectively form Nb-O ionic bond and Zr-O ionic bond with oxygen element, and the formation of ionic bond is beneficial to improving the structural stability of the ternary positive electrode material, thereby improving the cycle stability of the material. The bond energy of the Zr-O bond is higher than that of Ni-O, co-O and Mn-O bonds in a lithium nickel cobalt manganese oxide object phase, so that the structural stability and the cycle stability of the material are further improved.
In some embodiments, the lithium nickel cobalt manganese oxide satisfies the chemical formula Li αNiaCobMn（1-a-b）NbcZrdO2, wherein, alpha is more than or equal to 1.05 and less than or equal to 1.12,0.93 and more than or equal to a and less than or equal to 0.95,0.02, b is more than or equal to 0.04,0.1 and c is more than or equal to 0.2,0.2 and less than or equal to 0.4.
In some embodiments, the particle size D50 of the ternary positive electrode material satisfies: d50 is more than or equal to 9.5 mu m and less than or equal to 11.5 mu m.
A second aspect of the present application provides a method of preparing a ternary cathode material, useful in preparing the ternary cathode material of the first aspect of the present application, which may comprise the steps of:
s1, performing first sintering treatment on a first mixture containing a ternary precursor, a lithium source and a bimetallic oxide cluster powder containing lithium niobate and lithium zirconate to prepare a lithium nickel cobalt manganese oxide, wherein the bulk phase of the lithium nickel cobalt manganese oxide contains niobium element and zirconium element;
S2, performing second sintering treatment on a second mixture containing the lithium nickel cobalt manganese oxide, magnesium hydrogen phosphate (MgHPO 4) and polypyrrole (PPy), and forming a coating layer containing lithium phosphate and the polypyrrole on at least part of the surface of the lithium nickel cobalt manganese oxide to prepare the ternary positive electrode material.
In some embodiments, the ternary precursor includes nickel cobalt manganese complex carbonates, nickel cobalt manganese complex hydroxides, and the like.
In the step S1, the first mixture is subjected to a first sintering treatment, so that the bi-metal oxide cluster powder containing lithium niobate and lithium zirconate is decomposed to form Nb 5+ and Zr 4+, and Nb 5+ and Zr 4+ diffuse into the bulk phase of the lithium nickel cobalt manganese oxide at high temperature and combine with oxygen in the bulk phase to form nb—o bonds and zr—o bonds. In the step S2, the second mixture is subjected to a second sintering treatment, mgHPO 4 is decomposed into Mg 2P2O7 in the first step, then the phosphate-based material reacts with residual Li + to form lithium phosphate, and Mg 2+ is doped into a shallow surface layer of lithium nickel cobalt manganese oxide; meanwhile, polypyrrole flows in a melting way and forms a coating on at least part of the surface of the lithium nickel cobalt manganese oxide, so that the ternary anode material is prepared.
In the preparation method of the application, the bimetallic oxide cluster containing lithium niobate and lithium zirconate used in the step S1 has small granularity and high activity and can fully react with the ternary precursor and the lithium source; in addition, the bi-metal oxide cluster also maintains the specific proportion of the lithium niobate and the lithium zirconate applied during preparation, and can fully exert the modification effect of zirconium and niobium in the lithium nickel cobalt manganese layered material, thereby improving the stability of electrochemical performance output of the ternary positive electrode material, and particularly improving the cycling stability of the material under high voltage.
In addition, the bimetallic oxide cluster used in the step S1 has larger specific surface area and higher material activity, and can react with the ternary precursor and the lithium source more fully, so that better radial growth effect of the volatilized niobium element on the secondary sphere can be achieved, the stacking compactness of the spherical particle structure of the lithium nickel cobalt manganese oxide is improved, and the structural stability of the prepared ternary positive electrode material is improved. During the second sintering process of step S2, mg 2+ diffuses into the shallow surface layer of the lithium nickel cobalt manganese oxide and (P 2O7）4- reacts with the lithium source to form a lithium phosphate fast ion conductor, thereby facilitating the reduction of residual alkali.
In some embodiments, the particle size D50 of the lithium niobate and lithium zirconate containing bi-metal oxide cluster powder is 0.1 μm or less.
In some embodiments, the molar ratio of the lithium niobate to the lithium zirconate in the bimetallic oxide cluster powder containing the lithium niobate and the lithium zirconate is 1 (1.6-2.0).
In some embodiments, the particle size D50 of the lithium nickel cobalt manganese oxide is 9.2 μm to 11 μm.
In some embodiments, the lithium source includes, but is not limited to, lithium hydroxide or lithium carbonate.
In some embodiments, the temperature of the first sintering process is 750 ℃ to 850 ℃.
In some embodiments, the time of the first sintering process is 10h to 15h.
In some embodiments, the oxygen concentration of the first sintering treatment is above 99%, and the furnace pressure is 20 Pa-25 Pa.
In some embodiments, the mass ratio of the magnesium hydrogen phosphate to the polypyrrole is 1 (1-1.5).
In some embodiments, the temperature of the second sintering process is 300 ℃ to 380 ℃.
The temperature of the second sintering treatment is in the range, so that polypyrrole can be fused and coated on the surface of lithium nickel cobalt manganese oxide, and the decomposition of magnesium hydrogen phosphate can be promoted to form a lithium phosphate fast ion conductor.
In some embodiments, the second sintering process is performed for a period of 12h to 15h.
In some embodiments, the oxygen concentration of the second sintering treatment is 97% or more, and the furnace pressure is 10pa to 18pa.
In some embodiments, the preparation method of the bi-metal oxide cluster powder containing lithium niobate and lithium zirconate may include the steps of:
S1', performing heat treatment on a mixture containing lithium niobate and lithium zirconate to prepare the bimetal oxide cluster powder containing lithium niobate and lithium zirconate.
In some embodiments, the molar ratio of the lithium niobate to the lithium zirconate is 1 (1.6-2.0).
In some embodiments, the temperature of the heat treatment is 450 ℃ to 550 ℃.
The temperature of the heat treatment is in this range, so that lithium niobate and lithium zirconate are not decomposed, thereby facilitating the formation of a double metal oxide cluster structure.
In some embodiments, the heat treatment time is 8-10 hours.
In some embodiments, the atmosphere of the heat treatment is air.
A third aspect of the application provides a lithium ion battery comprising a ternary cathode material according to the first aspect of the application or a ternary cathode material prepared by a method according to the second aspect of the application.
A fourth aspect of the application provides an electronic device comprising a lithium ion battery according to the third aspect of the application.
In some embodiments, the kind of the electronic device is not particularly limited, and may be any electronic device known in the art. For example, the electronic device may include, but is not limited to, an electric tool, an electric car, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable phone, a portable facsimile machine, a portable copier, a portable printer, and the like.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since numerous modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
S1, sintering a mixture of LiNbO 3 and Li 2ZrO3 at 450 ℃ in an air atmosphere, and grinding and sieving in a sand mill to obtain the bimetallic oxide cluster powder with the granularity D50=0.08 mu m. Wherein, the mol ratio of LiNbO 3 to Li 2ZrO3 is 1:1.6.
S2, weighing 0.95Co0.02Mn0.03(OH)2 g of Ni, namely, calculating the molar ratio of Ni 0.95Co0.02Mn0.03(OH)2 to lithium hydroxide according to Li/Me (Me is Ni, co and Mn) equal to 1.05, wherein the dosage of the bimetallic oxide cluster powder is 7000ppm, and uniformly mixing Ni 0.95Co0.02Mn0.03(OH)2, lithium hydroxide and the bimetallic oxide cluster powder according to the proportion. The oxygen concentration is adjusted to 99%, the furnace pressure is set to 20Pa, sintering is carried out for 12 hours at 770 ℃, and the lithium nickel cobalt manganese oxide with the granularity D50=10.0 μm is obtained after crushing and sieving.
S3, weighing 120g of lithium nickel cobalt manganese oxide, wherein the total consumption of MgHPO 4 and PPy is 5000ppm, and the mass ratio of MgHPO 4 to PPy is 1:1.5. The oxygen concentration is adjusted to 99%, the furnace pressure is set at 12Pa, the sintering is carried out for 12 hours at 350 ℃, and the ternary positive electrode material with the granularity D50=11.2 μm is obtained after crushing and sieving.
S4, demagnetizing and packaging the ternary positive electrode material to obtain a final product.
Example 2
Similar to the preparation of example 1, the main differences are: in step S1, the molar ratio of LiNbO 3 to Li 2ZrO3 was 1:1.8.
Example 3
Similar to the preparation of example 1, the main differences are: in step S1, a mixture of LiNbO 3 and Li 2ZrO3 is sintered at 500 ℃.
Example 4
S1, sintering a mixture of LiNbO 3 and Li 2ZrO3 in an air atmosphere at 500 ℃, and grinding and sieving in a sand mill to obtain the bimetallic oxide cluster powder with the granularity D50=0.08 mu m. Wherein, the mol ratio of LiNbO 3 to Li 2ZrO3 is 1:1.8.
S2, weighing 180g of Ni 0.95Co0.02Mn0.03 (OH), calculating Ni 0.95Co0.02Mn0.03 (OH) and lithium hydroxide according to a molar ratio of Li/Me (Me is Ni, co and Mn) equal to 1.05, wherein the dosage of the double metal oxide cluster powder is 7000ppm, and uniformly mixing Ni 0.95Co0.02Mn0.03 (OH), lithium hydroxide and the double metal oxide cluster powder according to the proportion. The oxygen concentration is adjusted to 99%, the furnace pressure is set to 25Pa, sintering is carried out for 12 hours at 800 ℃, and the lithium nickel cobalt manganese oxide with the granularity D50=10.0 μm is obtained after crushing and sieving.
S3, weighing 120g of lithium nickel cobalt manganese oxide, wherein the total consumption of MgHPO 4 and PPy is 6000ppm, and the mass ratio of MgHPO 4 to PPy is 1:1.5. The oxygen concentration is adjusted to 99%, the furnace pressure is set at 12Pa, the sintering is carried out for 12 hours at 350 ℃, and the ternary positive electrode material with the granularity D50=11.2 μm is obtained after crushing and sieving.
S4, demagnetizing and packaging the ternary positive electrode material to obtain a final product.
Example 5
Similar to the preparation of example 4, the main differences are: in step S2, sintering is carried out at 800 ℃ for 15 hours.
Example 6
Similar to the preparation of example 4, the main differences are: in step S2, the amount of the bimetal oxide cluster powder used was 8000ppm.
Example 7
S1, sintering a mixture of LiNbO 3 and Li 2ZrO3 in an air atmosphere at 550 ℃, and grinding and sieving in a sand mill to obtain the bimetallic oxide cluster powder with the granularity D50=0.08 mu m. Wherein, the mol ratio of LiNbO 3 to Li 2ZrO3 is 1:1.8.
S2, weighing 0.95Co0.02Mn0.03(OH)2 g of Ni, namely, calculating the molar ratio of Ni 0.95Co0.02Mn0.03(OH)2 to lithium hydroxide according to Li/Me (Me is Ni, co and Mn) equal to 1.05, wherein the dosage of the bimetallic oxide cluster powder is 9000ppm, and uniformly mixing Ni 0.95Co0.02Mn0.03(OH)2, lithium hydroxide and the bimetallic oxide cluster powder according to the proportion. The oxygen concentration is adjusted to 99%, the furnace pressure is set to 25Pa, sintering is carried out for 15h at 810 ℃, and the lithium nickel cobalt manganese oxide with the granularity D50=10.0 μm is obtained after crushing and sieving.
S3, weighing 120g of lithium nickel cobalt manganese oxide, wherein the total consumption of MgHPO 4 and PPy is 5000ppm, and the mass ratio of MgHPO 4 to PPy is 1:1.5. The oxygen concentration is adjusted to 99%, the furnace pressure is set to 10Pa, the sintering is carried out for 12 hours at 350 ℃, and the ternary positive electrode material with the granularity D50=11.2 μm is obtained after crushing and sieving.
S4, demagnetizing and packaging the ternary positive electrode material to obtain a final product.
Example 8
Similar to the preparation of example 7, the main differences are: in step S3, the total amount of MgHPO 4 and PPy was 6000ppm.
Comparative example 1
Similar to the preparation of example 1, the main differences are: step S1 was omitted and the bimetallic oxide cluster powder in step S2 was replaced with an equal amount of a mixture of LiNbO 3 and Li 2ZrO3, i.e. the mixture of LiNbO 3 and Li 2ZrO3 was used in an amount of 7000ppm and the molar ratio of LiNbO 3 to Li 2ZrO3 was 1:1.6.
Comparative example 2
Similar to the preparation of example 1, the main differences are: in step S3, the PPy is replaced with an equal amount of MgHPO 4.
Comparative example 3
Similar to the preparation of example 1, the main differences are: in step S3, PPy is replaced with an equal amount of polyaniline.
Comparative example 4
Similar to the preparation of example 1, the main differences are: in step S3, mgHPO 4 is replaced with an equal amount of PPy.
Comparative example 5
Similar to the preparation of example 1, the main differences are: in step S3, mgHPO 4 is replaced with an equal amount of CaHPO 4.
The ternary cathode materials in the above examples and comparative examples were prepared into button cells, and electrochemical performance tests were performed, as follows:
Mixing the prepared anode material powder with acetylene black, carbon nano tubes and polyvinylidene fluoride according to the mass ratio of 95:2:1:2, adding a proper amount of N-methyl pyrrolidone as a dispersing agent, and grinding into slurry; and then uniformly coating the slurry on an aluminum foil, drying the aluminum foil in vacuum at 120 ℃ for 12 hours, rolling the dried pole piece by a pair roller, cutting the aluminum foil by a slicer, and cutting the aluminum foil into round pole pieces with the diameter of 10mm, wherein the loading amount of the active material is controlled to be about 10mg/cm 2. Assembling half cells in an argon atmosphere glove box, wherein the water partial pressure is less than or equal to 0.1ppm, and the oxygen partial pressure is less than or equal to 0.1ppm; the metal lithium is used as a counter electrode, 1mol/L LiPF 6 (EC/DMC, volume ratio is 1:1) solution is used as electrolyte, and the assembly specification is CR2032 type button cell.
The ternary cathode materials prepared in examples 1 to 8 and comparative examples 1 to 5 or further prepared lithium ion batteries were subjected to related performance tests, and the test results are shown in table 1 below.
The test conditions or test standards of each performance test item are as follows:
(1) Morphology characterization: the morphology of the samples was observed using a Scanning Electron Microscope (SEM).
(2) Particle size testing method: particle size of each sample was measured using a particle size analyzer, specific test parameters: the solvent refractive index was 1.33 and the test cycle was 3 times.
(3) Test of first charge/discharge specific capacity and direct current internal resistance (DCR): charging and discharging the button cell at 25 ℃ by using a constant current charging and discharging mode, charging to 0.05 ℃ by using constant current of 0.1 to 4.7V and constant voltage of 4.7V, and discharging to 3.0V by using constant current of 0.1C to obtain primary discharge specific capacity and primary DCR; the charge and discharge equipment is a blue charge and discharge instrument, and the discharge specific capacity and DCR after 50 times of test cycle are adopted;
50 cycle capacity retention= (50 discharge specific capacity/first discharge specific capacity) ×100%.
(4) And (3) multiplying power performance test:
The prepared battery is charged to 4.7V at constant current and constant voltage of 0.1C, after cut-off current is 0.05C, the battery is kept still for 5min, and then is discharged to 3.0V at constant current of 0.1C/1C, and the discharge capacity under different multiplying powers is recorded.
(5) Residual Li + test:
5g of the sample is weighed and dissolved in deionized water, magnetically stirred for 5min, suction filtered, separated to obtain filtrate, and the contents of LiOH and Li 2CO3 in the filtrate are measured by adopting a potentiometric titrator, and the content of soluble lithium (wt%) =LiOH (wt%) ×6/94.23.95+Li 2CO3 (wt%) ×2×6.94/73.89 is calculated.
TABLE 1
As can be seen from Table 1, compared with comparative examples 1 to 5, the ternary cathode materials prepared in examples 1 to 8 have higher specific capacity, lower DCR for the first time, excellent rate performance, lower residual alkali and stronger application performance.
The content of Li 2ZrO3 in the bimetallic oxide cluster in the example 2 is increased, the interlayer spacing can be increased after Zr 4+ is doped into the crystal lattice, the migration channel of Li + is widened, and the bonding energy of Zr-O is stronger than that of (Ni, co and Mn) -O, so that the capacity retention rate, the first DCR and the rate capability of the example 2 are all improved compared with those of the example 1.
The sintering temperature of the mixture of LiNbO 3 and Li 2ZrO3 in example 3 is advantageously increased to enhance the bonding force between the two structures, so that the cycle retention and rate performance of example 3 are both improved as compared to example 1.
Since the increase in the sintering temperature and the increase in the sintering time in step S2 in example 5 can suppress cation mixing, the specific discharge capacity in example 5 is significantly improved as compared with example 4.
In the embodiment 6, the content of the bimetallic oxide cluster powder is increased, the migration channel of Li + can be widened by Zr 4+ doping, the bonding capability of Zr-O bonds is strong, and the radial growth of lithium nickel cobalt manganese oxide can be promoted by Nb 5+ doping, so that the capacity retention rate, the first DCR and the multiplying power performance of the embodiment 6 are obviously improved compared with those of the embodiment 4.
The total amount of MgHPO 4 and PPy in example 8 was increased, mgHPO 4 was able to react with Li + to form a fast ion conductor, was able to reduce residual alkali and increase conductivity, and thus the rate performance of example 8 was improved and residual Li + was reduced compared to example 7.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (10)
1. The ternary positive electrode material is characterized by comprising a lithium nickel cobalt manganese oxide and a coating layer coated on at least part of the surface of the lithium nickel cobalt manganese oxide, wherein the bulk phase of the lithium nickel cobalt manganese oxide contains niobium and zirconium, and the coating layer contains lithium phosphate and polypyrrole.
2. The ternary cathode material of claim 1, wherein at least one of the following conditions is satisfied:
(1) The total content of the niobium element and the zirconium element in the ternary positive electrode material is 70000 ppm-9000 ppm;
(2) The total content of the lithium phosphate and the polypyrrole in the ternary positive electrode material is 4000 ppm-6000 ppm;
(3) The thickness of the coating layer is 15 nm-20 nm.
3. The ternary cathode material according to claim 1 or 2, wherein the shallow surface layer of lithium nickel cobalt manganese oxide contains magnesium element;
Optionally, the content of the magnesium element in the ternary positive electrode material is 1500 ppm-3000 ppm.
4. The ternary cathode material of claim 1 or 2, wherein at least one of the following conditions is satisfied:
(1) The bulk phase of the lithium nickel cobalt manganese oxide contains ionic bonds formed by the niobium element and the zirconium element and oxygen element respectively;
(2) The bulk phase of the lithium nickel cobalt manganese oxide comprises Nb 5+ and Zr 4+;
(3) The lithium nickel cobalt manganese oxide satisfies the chemical formula Li αNiaCobMn（1-a-b）NbcZrdO2, wherein alpha is more than or equal to 1.05 and less than or equal to 1.12,0.93 and a is more than or equal to 0.95,0.02 and less than or equal to 0.04,0.1, c is more than or equal to 0.2,0.2 and d is more than or equal to 0.4;
(4) The particle size D50 of the ternary positive electrode material meets the following conditions: d50 is more than or equal to 9.5 mu m and less than or equal to 11.5 mu m.
5. A method of preparing a ternary positive electrode material, comprising:
Performing first sintering treatment on a first mixture containing a ternary precursor, a lithium source and a bimetallic oxide cluster powder containing lithium niobate and lithium zirconate to prepare a lithium nickel cobalt manganese oxide, wherein the bulk phase of the lithium nickel cobalt manganese oxide contains niobium element and zirconium element;
And performing second sintering treatment on the second mixture containing the lithium nickel cobalt manganese oxide, magnesium hydrogen phosphate and polypyrrole, and forming a coating layer containing lithium phosphate and the polypyrrole on at least part of the surface of the lithium nickel cobalt manganese oxide to prepare the ternary positive electrode material.
6. The method of claim 5, wherein at least one of the following conditions is satisfied:
(1) The particle diameter D50 of the bimetallic oxide cluster powder containing lithium niobate and lithium zirconate is below 0.1 mu m;
(2) In the bimetallic oxide cluster powder containing lithium niobate and lithium zirconate, the molar ratio of the lithium niobate to the lithium zirconate is 1 (1.6-2.0);
(3) The particle size D50 of the lithium nickel cobalt manganese oxide is 9.2-11 mu m;
(4) The temperature of the first sintering treatment is 750-850 ℃;
(5) The time of the first sintering treatment is 10-15 h.
7. The method according to claim 5 or 6, wherein at least one of the following conditions is fulfilled:
(1) In the second mixture, the mass ratio of the magnesium hydrophosphate to the polypyrrole is 1 (1-1.5);
(2) The temperature of the second sintering treatment is 300-380 ℃;
(3) The time of the second sintering treatment is 12-15 h.
8. The method according to claim 5 or 6, wherein the preparation method of the lithium niobate and lithium zirconate containing double metal oxide cluster powder comprises the steps of:
performing heat treatment on a mixture containing lithium niobate and lithium zirconate to prepare the bimetal oxide cluster powder containing lithium niobate and lithium zirconate;
optionally, the molar ratio of the lithium niobate to the lithium zirconate is 1 (1.6-2.0);
Optionally, the temperature of the heat treatment is 450-550 ℃;
Optionally, the heat treatment time is 8-10 h.
9. A lithium ion battery comprising the ternary cathode material of any one of claims 1-4 or prepared by the method of any one of claims 5-8.
10. An electronic device comprising the battery of claim 9.
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