CN114014381A - Interface composite modification method of positive electrode material, positive electrode material and application - Google Patents
Interface composite modification method of positive electrode material, positive electrode material and application Download PDFInfo
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Abstract
The invention provides an interface composite modification method of a positive electrode material, the positive electrode material and application, wherein the interface composite modification method comprises the following steps: and the precursor, the lithium source and the nano oxide are mixed for the first time and then calcined to obtain a sintering material, and the sintering material, the inducer and the boron source are mixed for the second time and then calcined to obtain the single crystal anode material. The interface composite modification method provided by the invention reduces the residual alkali content on the surface of the anode material in a co-coating mode, thereby improving the cycle stability, rate capability and thermal stability of the anode material.
Description
Technical Field
The invention belongs to the technical field of anode materials, and relates to an interface composite modification method of an anode material, the anode material and application.
Background
At present, with the rapid development of the new energy automobile industry, higher requirements are placed on the energy density and the power density of the lithium ion battery, and the positive electrode material is one of the most critical materials for improving the energy density of the lithium ion battery, so that the preparation of the positive electrode material with high specific capacity becomes a current research hotspot. The ternary layered positive electrode material has the advantages of high specific discharge capacity, good cycle performance, low cost and the like, the specific discharge capacity is gradually improved along with the improvement of the Ni content, and when the Ni content is improved by more than 80%, the specific discharge capacity can reach 200mAh/g, so that the ternary layered positive electrode material has the remarkable energy density advantage.
As a hot spot, a series of researches on the high-nickel ternary cathode material have been carried out by experts at home and abroad, and in the research process, the material is found to have some defects, such as: the surface stability of the high-nickel ternary nickel cobalt lithium manganate (NCM) anode material is poor, and the high-nickel ternary nickel cobalt lithium manganate is easy to react with electrolysis in a circulation process, so that the gas generation of the battery is caused in the circulation process, and further the circulation performance of the battery is influenced.
The main reason for gas generation is that the high nickel positive electrode material has strong reactivity and generates gas due to chemical reaction during charging when directly contacting with the electrolyte. In order to improve this problem, many researchers have focused on coating the positive electrode material to form a relatively stable coating layer to inhibit side reactions with the electrolyte solution and thus reduce the gas generation of the cell. In recent years, various research efforts on coating have provided the art with a number of valuable coating methods. The coating method adopted in the prior art comprises wet coating and dry coating, wherein the wet coating only plays a role of uniform coating actually and does not have strong chemical bonding effect, and the subsequent coating firing is easy to form the defect of incomplete local coating; the dry coating has higher requirements on the mixing, and once the mixing is uneven, the defect of uneven local coating can be caused.
The conventional technique has two main disadvantages: firstly, the side reaction of electrolyte and anode material is inhibited through surface coating, and the gas generation in the battery cycle process is reduced. However, in the industrial production, the surfaces of the particles of the positive electrode material are basically coated in an island shape or a sheet shape, or the coating layers are loose, so that the side reaction of the electrolyte and the positive electrode material is difficult to completely avoid. Secondly, if the coating layer is added, the specific discharge capacity, particularly the rate capability, is obviously reduced.
CN108321380A discloses a gallium oxide coated high-nickel ternary lithium battery positive electrode material and a preparation method thereof, wherein a high-nickel ternary positive electrode precursor material is prepared by a coprecipitation method, then the precursor material is soaked and stirred in boiling water, metal gallium is added dropwise until the surface of the precursor is completely coated by white jelly, and the precursor is filtered, mixed with a lithium source, subjected to ball milling, rapidly heated and calcined to obtain the gallium oxide coated high-nickel ternary lithium battery positive electrode material.
CN109888235A discloses a graded high-nickel ternary positive electrode material, a preparation method and application thereof. The graded high-nickel ternary cathode material is prepared by the following method: 1) mixing a high-nickel polycrystalline precursor, anhydrous LiOH and a doping additive, sintering, mixing the obtained product with a coating additive, and sintering to obtain a high-nickel polycrystalline material; 2) mixing the ternary single crystal precursor, a lithium source and a doping additive, sintering, mixing the obtained product with a coating additive, and sintering to obtain a ternary single crystal material; 3) mixing the high-nickel polycrystalline material with the ternary single crystal material, or mixing the mixture with the coating additive and then sintering.
CN111517378A discloses a high nickel cathode material, a preparation method and an application thereof, wherein the method comprises: (1) mixing a ternary precursor containing nickel, cobalt and manganese with a lithium salt, and performing primary sintering, washing and dehydration to obtain a first dehydrated material; (2) slurrying and mixing the first dehydrated material and a mixture containing a coating raw material and a stabilizer, and dehydrating to obtain a second dehydrated material; (3) drying the second dehydrated material so as to enable the coating raw material to generate a hydrolysis reaction and coat the surface of the second dehydrated material; (4) and (4) carrying out secondary sintering on the coated material obtained in the step (3) so as to obtain the high-nickel anode material.
The most common solution to the above problems is to coat the positive electrode material and design a complex structure to improve the cycle performance and rate capability of the material, but the improvement effect is not ideal.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an interface composite modification method of a positive electrode material, the positive electrode material and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an interfacial recombination modification method for a positive electrode material, which is characterized in that the interfacial recombination modification method includes:
and the precursor, the lithium source and the nano oxide are mixed for the first time and then calcined to obtain a sintering material, and the sintering material, the inducer and the boron source are mixed for the second time and then calcined to obtain the single crystal anode material.
The interface composite modification method provided by the invention reduces the residual alkali content on the surface of the anode material in a co-coating mode, thereby improving the cycle stability, rate capability and thermal stability of the anode material. Specifically, the method comprises the following steps: (1) the nano oxide is added, so that the structural stability of the material is improved, and the cycle performance is improved; (2) promoting oxygen release reaction on the surface of the particles of the anode material under the thermal decomposition action of the inducer to form a spinel structure with stable structure, and inhibiting the reaction with the electrolyteSide reaction, reduce gas production, spinel structure formed on the surface is favorable for the desorption of lithium ions, and the rate capability is improved; (3) the boron source is thermally decomposed to generate Li with residual alkali on the surface of the anode material2O-B2O3And simultaneously generates boron nitride with a thermal decomposition product of the inducer to form a composite cladding layer of two borides, which is beneficial to further inhibiting the occurrence of side reaction.
As a preferable technical scheme of the invention, the chemical general formula of the precursor is NixCoyMnz(OH)2X is more than or equal to 0.8, x + y + z is 1, y is more than 0, and z is less than 1; for example, x can be 0.8, 0.82, 0.84, 0.86, 0.88, 0.90, 0.92, 0.94, 0.96 or 0.98, y can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, and z can be 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8 or 1.9, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the lithium source and the precursor are mixed in a molar ratio of Li (Ni + Co + Mn) of 1 to 1.15, for example, 1.0, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.1, 1.11, 1.12, 1.13, 1.14 or 1.15, but not limited to the values listed, and other values not listed within the range of values are equally applicable.
Preferably, the nano-oxide is added in an amount of 500 to 3000ppm, for example, 500ppm, 1000ppm, 1500ppm, 2000ppm, 2500ppm or 3000ppm of the total mass of the precursor and the lithium source, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the nano-oxide comprises any one of or a combination of at least two of zirconia, titania, tungsten oxide, molybdenum oxide, alumina, or yttria.
Preferably, the time for the first mixing is 10-30 min, such as 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In a preferred embodiment of the present invention, the calcination process is performed in an oxygen atmosphere.
Preferably, the oxygen flow rate of the oxygen atmosphere is 5 to 20L/min, such as 5L/min, 6L/min, 7L/min, 8L/min, 9L/min, 10L/min, 11L/min, 12L/min, 13L/min, 14L/min, 15L/min, 16L/min, 17L/min, 18L/min, 19L/min or 20L/min, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the oxygen concentration of the oxygen atmosphere is more than or equal to 99.99%.
In a preferred embodiment of the present invention, the heating rate of the calcination is 2 to 5 ℃/min, and may be, for example, 2.0 ℃/min, 2.2 ℃/min, 2.4 ℃/min, 2.6 ℃/min, 2.8 ℃/min, 3.0 ℃/min, 3.2 ℃/min, 3.4 ℃/min, 3.6 ℃/min, 3.8 ℃/min, 4.0 ℃/min, 4.2 ℃/min, 4.4 ℃/min, 4.6 ℃/min, 4.8 ℃/min, or 5.0 ℃/min, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the temperature of the calcination is 800 to 950 ℃, for example 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃ or 950 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the calcination is carried out for a holding time of 5 to 15 hours, for example, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the sintered material is obtained by sieving the product after calcination.
In a preferred embodiment of the present invention, the mass ratio of the sintering material, the inducer and the boron source is 1 (0.2 to 1.0): (0.1 to 0.5), and may be, for example, 1:0.2:0.1, 1:0.3:0.1, 1:0.4:0.2, 1:0.5:0.2, 1:0.6:0.3, 1:0.7:0.3, 1:0.8:0.4, 1:0.9:0.4 or 1:1:0.5, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
The invention particularly limits the mass ratio of the sintering material to the inducer to the boron source to be 1 (0.2-1.0) to (0.1-0.5), and when the addition amount of the inducer is too high, the primary particle size is larger, because a large amount of heat energy is generated in the reaction process of the inducer, the primary particle is grown; when the addition amount of the inducer is too low, the effect of improving gas production is not achieved, because the content of the formed boron nitride is low; when the addition amount of the boron source is too high, the specific discharge capacity is low, and the formed coating layer is too thick, so that the transmission of lithium ions is reduced; when the amount of the boron source added is too low, the gas yield is too high because the amount of the formed coating is low.
Preferably, the inducer comprises cyanuric acid, dicyandiamide, hydroxyethyl urea or melamine.
Preferably, the boron source comprises boric acid and/or boron oxide.
Preferably, the time of the secondary mixing is 10-30 min, for example, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
As a preferred technical scheme of the invention, the roasting process is carried out in a protective atmosphere.
Preferably, the protective atmosphere comprises a nitrogen atmosphere or an argon atmosphere.
Preferably, the temperature rise rate of the baking process is 2-5 ℃/min, for example, 2.0 ℃/min, 2.5 ℃/min, 3.0 ℃/min, 3.5 ℃/min, 4.0 ℃/min, 4.5 ℃/min or 5.0 ℃/min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the temperature of the baking is 300 to 700 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
The invention particularly limits the roasting temperature to be 300-700 ℃, and when the roasting temperature exceeds 700 ℃, the specific discharge capacity and the rate capability are low, because the cladding material and the body generate side reaction to form a hetero phase, the extraction of lithium ions is inhibited; when the firing temperature is lower than 300 ℃, the gas yield is too high because the formed coating layer is not tightly bonded to the bulk.
Preferably, the baking holding time is 4-20 h, for example, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme, the interface composite modification method comprises the following steps:
(I) precursor NixCoyMnz(OH)2Mixing the lithium source and the nano oxide for 10-30 min at one time, feeding the lithium source and the precursor according to the molar ratio of Li (Ni + Co + Mn) being 1-1.15, wherein the addition amount of the nano oxide is 500-3000 ppm of the total mass of the precursor and the lithium source;
(II) placing the materials after primary mixing in an oxygen atmosphere with the oxygen flow of 5-20L/min, heating to 800-950 ℃ at the heating rate of 2-5 ℃/min, preserving heat for 5-15 h, and sieving to sinter the materials;
and (III) secondarily mixing the sintering material, the inducer and the boron source according to the mass ratio of 1 (0.2-1.0) to (0.1-0.5) for 10-30 min, then placing in a protective atmosphere, raising the temperature to 300-700 ℃ at the temperature rise rate of 2-5 ℃/min, preserving the temperature for 4-20 h, and sieving to obtain the single crystal anode material.
In a second aspect, the invention provides a cathode material prepared by the interfacial composite modification method of the first aspect.
In a preferred embodiment of the present invention, the particle size D50 of the positive electrode material is 3 to 4 μm, and may be, for example, 3.0 μm, 3.1 μm, 3.2 μm, 3.3 μm, 3.4 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm or 4.0 μm, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the specific surface area of the positive electrode material is 0.5-0.8 m2Per g, may be, for example, 0.5m2/g、0.55m2/g、0.6m2/g、0.65m2/g、0.7m2/g、0.75m2G or 0.8m2In the following description,/g is not limited to the values listed, but other values not listed in the numerical range are equally applicable.
Preferably, the positive electrode material has a pH of 11.8 or less, and may be, for example, 10, 10.2, 10.4, 10.6, 10.8, 11.0, 11.2, 11.4, 11.6 or 11.8, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the surface residual alkali of the positive electrode material is 3500ppm or less, and may be 3000ppm, 3050ppm, 3100ppm, 3150ppm, 3200ppm, 3250ppm, 3300ppm, 3350ppm, 3400ppm, 3450ppm or 3500ppm, for example, but is not limited to the values listed, and other values not listed in the numerical range may be used.
In a third aspect, the present invention provides a lithium battery comprising a positive electrode, a separator and a negative electrode stacked in this order, the positive electrode comprising the positive electrode material of the first aspect.
Compared with the prior art, the invention has the beneficial effects that:
the interface composite modification method provided by the invention reduces the residual alkali content on the surface of the anode material in a co-coating mode, thereby improving the cycle stability, rate capability and thermal stability of the anode material. Specifically, the method comprises the following steps: (1) the nano oxide is added, so that the structural stability of the material is improved, and the cycle performance is improved; (2) under the thermal decomposition action of the inducer, the oxygen release reaction is promoted to occur on the particle surface of the anode material, a spinel structure with a stable structure is formed, the side reaction with the electrolyte is inhibited, the gas generation is reduced, the spinel structure formed on the surface is beneficial to the extraction of lithium ions, and the rate capability is improved; (3) the boron source is thermally decomposed to generate Li with residual alkali on the surface of the anode material2O-B2O3And simultaneously generates boron nitride with a thermal decomposition product of the inducer to form a composite cladding layer of two borides, which is beneficial to further inhibiting the occurrence of side reaction.
Drawings
FIG. 1 is an electron micrograph of a single crystal lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 of the present invention;
FIG. 2 is a 50-cycle curve of the single-crystal lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides an interface composite modification method of a nickel cobalt lithium manganate positive electrode material, which specifically comprises the following steps:
(I) precursor Ni0.8Co0.1Mn0.1(OH)2、Li(OH)2Mixing with nanometer zirconia for 10min in one time, Li (OH)2And the precursor is fed according to the mol ratio of Li (Ni + Co + Mn) ═ 1, the adding quantity of nano zirconia is that of the precursor and Li (OH)2500ppm of the total mass;
(II) placing the materials after primary mixing in an oxygen atmosphere (the oxygen concentration is more than or equal to 99.99%) with the oxygen flow of 5L/min, heating to 800 ℃ at the heating rate of 2 ℃/min, preserving the heat for 15h, and sieving the sintered materials;
(III) mixing the sintering material, cyanuric acid and boric acid for 10min twice according to the mass ratio of 1:0.2:0.3, then placing in a nitrogen atmosphere, heating to 300 ℃ at the heating rate of 2 ℃/min, preserving heat for 20h, and sieving to obtain the single crystal nickel cobalt lithium manganate positive electrode material.
Example 2
The embodiment provides an interface composite modification method of a nickel cobalt lithium manganate positive electrode material, which specifically comprises the following steps:
(I) precursor Ni0.82Co0.08Mn0.1(OH)2、Li(OH)2Mixing with nanometer titanium oxide for 14min in one time, Li (OH)2And the precursor is fed according to the mol ratio of Li (Ni + Co + Mn) to 1.05, and is subjected to nano oxidationThe addition of titanium is 1000ppm of the total mass of the precursor and Li (OH) 2;
(II) placing the materials after primary mixing in an oxygen atmosphere (the oxygen concentration is more than or equal to 99.99%) with the oxygen flow of 8L/min, heating to 830 ℃ at the heating rate of 2.5 ℃/min, preserving heat for 13h, and sieving to sinter the materials;
(III) secondarily mixing the sintering material, dicyandiamide and boron oxide for 14min according to the mass ratio of 1:0.4:0.3, then placing in a nitrogen atmosphere, heating to 380 ℃ at the heating rate of 2.5 ℃/min, preserving heat for 18h, and sieving to obtain the single crystal lithium nickel cobalt manganese oxide cathode material.
An electron micrograph of the single crystal lithium nickel cobalt manganese oxide cathode material is shown in figure 1.
Example 3
The embodiment provides an interface composite modification method of a nickel cobalt lithium manganate positive electrode material, which specifically comprises the following steps:
(I) precursor Ni0.85Co0.05Mn0.1(OH)2、Li(OH)2Mixing with nanometer tungsten oxide for 18min, Li (OH)2And the precursor is fed according to the mol ratio of Li (Ni + Co + Mn) to 1.08, and the adding amount of the nano tungsten oxide is 1500ppm of the total mass of the precursor and Li (OH) 2;
(II) placing the materials after primary mixing in an oxygen atmosphere (the oxygen concentration is more than or equal to 99.99%) with the oxygen flow of 10L/min, heating to 860 ℃ at the heating rate of 3 ℃/min, preserving heat for 10h, and sieving to sinter the materials;
(III) secondarily mixing the sintering material, hydroxyethyl urea and boric acid according to the mass ratio of 1:0.5:0.4 for 18min, then placing in an argon atmosphere, heating to 460 ℃ at the heating rate of 3 ℃/min, preserving heat for 15h, and sieving to obtain the single crystal nickel cobalt lithium manganate positive electrode material.
Example 4
The embodiment provides an interface composite modification method of a nickel cobalt lithium manganate positive electrode material, which specifically comprises the following steps:
(I) precursor Ni0.88Co0.06Mn0.06(OH)2、Li(OH)2Mixing with nanometer molybdenum oxide for 22min, Li (OH)2And the precursor is fed according to the mol ratio of Li (Ni + Co + Mn) to 1.1, and the adding amount of the nano molybdenum oxide is 2000ppm of the total mass of the precursor and Li (OH) 2;
(II) placing the materials after primary mixing in an oxygen atmosphere (the oxygen concentration is more than or equal to 99.99%) with the oxygen flow of 13L/min, heating to 900 ℃ at the heating rate of 3.5 ℃/min, preserving heat for 9h, and sieving to sinter the materials;
(III) mixing the sintering material, melamine and boron oxide for 22min twice according to the mass ratio of 1:0.6:0.5, then placing the mixture in an argon atmosphere, heating to 540 ℃ at the heating rate of 3.5 ℃/min, preserving heat for 12h, and sieving to obtain the single crystal nickel cobalt lithium manganate positive electrode material.
Example 5
The embodiment provides an interface composite modification method of a nickel cobalt lithium manganate positive electrode material, which specifically comprises the following steps:
(I) precursor Ni0.9Co0.05Mn0.05(OH)2、Li(OH)2Mixing with nanometer alumina for 26min, Li (OH)2And the precursor is fed according to the mol ratio of Li (Ni + Co + Mn) to 1.13, and the adding amount of the nano alumina is 2500ppm of the total mass of the precursor and Li (OH) 2;
(II) placing the materials after primary mixing in an oxygen atmosphere (oxygen concentration is more than or equal to 99.99%) with the oxygen flow of 16L/min, heating to 920 ℃ at the heating rate of 4 ℃/min, preserving heat for 7h, and sieving to sinter the materials;
(III) mixing the sintering material, cyanuric acid and boric acid for 26min twice according to the mass ratio of 1:0.8:0.1, then placing in a nitrogen atmosphere, heating to 620 ℃ at the heating rate of 4 ℃/min, preserving heat for 8h, and sieving to obtain the single crystal nickel cobalt lithium manganate positive electrode material.
Example 6
The embodiment provides an interface composite modification method of a nickel cobalt lithium manganate positive electrode material, which specifically comprises the following steps:
(I) precursor Ni0.92Co0.05Mn0.03(OH)2、Li(OH)2Mixing with nanometer yttrium oxide for 30min at one time, Li (OH)2And the precursor is fed according to the mol ratio of Li (Ni + Co + Mn) 1.15, the adding amount of the nano yttrium oxide is that of the precursor and Li (OH)23000ppm of the total mass;
(II) placing the materials after primary mixing in an oxygen atmosphere (the oxygen concentration is more than or equal to 99.99%) with the oxygen flow of 20L/min, heating to 950 ℃ at the heating rate of 5 ℃/min, preserving heat for 5h, and sieving to sinter the materials;
(III) mixing the sintering material, cyanuric acid and boron oxide for 30min twice according to the mass ratio of 1:1:0.2, then placing in a nitrogen atmosphere, heating to 700 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, and sieving to obtain the single crystal nickel cobalt lithium manganate positive electrode material.
Example 7
The embodiment provides an interfacial composite modification method of a nickel cobalt lithium manganate positive electrode material, which is different from the embodiment 1 in that in the step (III), a sintering material, an inducer and a boron source are secondarily mixed according to the mass ratio of 1:1.2:0.3, and other process parameters and operation steps are completely the same as those in the embodiment 1.
Example 8
The embodiment provides an interfacial composite modification method of a nickel cobalt lithium manganate positive electrode material, which is different from the embodiment 1 in that in the step (III), a sintering material, an inducer and a boron source are secondarily mixed according to the mass ratio of 1:0.1:0.3, and other process parameters and operation steps are completely the same as those in the embodiment 1.
Example 9
The embodiment provides an interfacial composite modification method of a nickel cobalt lithium manganate positive electrode material, which is different from the embodiment 1 in that in the step (iii), a sintering material, an inducer and a boron source are secondarily mixed according to a mass ratio of 1:0.2:0.8, and other process parameters and operation steps are completely the same as those in the embodiment 1.
Example 10
The embodiment provides an interfacial composite modification method of a nickel cobalt lithium manganate positive electrode material, which is different from the embodiment 1 in that in the step (iii), a sintering material, an inducer and a boron source are secondarily mixed according to a mass ratio of 1:0.2:0.05, and other process parameters and operation steps are completely the same as those in the embodiment 1.
Example 11
The embodiment provides an interfacial composite modification method of a nickel cobalt lithium manganate positive electrode material, which is different from the embodiment 1 in that the sintering temperature in the step (III) is 250 ℃, and other process parameters and operation steps are completely the same as those in the embodiment 1.
Example 12
The embodiment provides an interfacial composite modification method of a nickel cobalt lithium manganate positive electrode material, which is different from the embodiment 1 in that the sintering temperature in the step (III) is 750 ℃, and other process parameters and operation steps are completely the same as those in the embodiment 1.
Comparative example 1
The embodiment provides an interface composite modification method of a nickel cobalt lithium manganate positive electrode material, which specifically comprises the following steps:
(I) precursor Ni0.8Co0.1Mn0.1(OH)2And Li (OH)2Mixing for 10min once, Li (OH)2And the precursor is fed according to the mol ratio of Li (Ni + Co + Mn) to 1;
(II) placing the materials after primary mixing in an oxygen atmosphere (the oxygen concentration is more than or equal to 99.99%) with the oxygen flow of 5L/min, heating to 800 ℃ at the heating rate of 2 ℃/min, preserving the heat for 15h, and sieving the sintered materials;
(III) mixing the sintering material, cyanuric acid and boric acid for 10min twice according to the mass ratio of 1:0.2:0.3, then placing in a nitrogen atmosphere, heating to 300 ℃ at the heating rate of 2 ℃/min, preserving heat for 20h, and sieving to obtain the single crystal nickel cobalt lithium manganate positive electrode material.
Comparative example 2
The embodiment provides an interface composite modification method of a nickel cobalt lithium manganate positive electrode material, which specifically comprises the following steps:
(I) precursor Ni0.8Co0.1Mn0.1(OH)2、Li(OH)2Mixing with nanometer zirconia for 10min in one time, Li (OH)2And the precursor is fed according to the mol ratio of Li (Ni + Co + Mn) ═ 1, the adding quantity of nano zirconia is that of the precursor and Li (OH)2500ppm of the total mass;
(II) placing the materials after primary mixing in an oxygen atmosphere (the oxygen concentration is more than or equal to 99.99%) with the oxygen flow of 5L/min, heating to 800 ℃ at the heating rate of 2 ℃/min, preserving the heat for 15h, and sieving the sintered materials;
(III) secondarily mixing the sintering material and cyanuric acid according to the mass ratio of 1:0.2 for 10min, then placing in a nitrogen atmosphere, heating to 300 ℃ at the heating rate of 2 ℃/min, preserving the heat for 20h, and sieving to obtain the single crystal nickel cobalt lithium manganate positive electrode material.
Comparative example 3
The embodiment provides an interface composite modification method of a nickel cobalt lithium manganate positive electrode material, which specifically comprises the following steps:
(I) precursor Ni0.8Co0.1Mn0.1(OH)2、Li(OH)2Mixing with nanometer zirconia for 10min in one time, Li (OH)2And the precursor is fed according to the mol ratio of Li (Ni + Co + Mn) ═ 1, the adding quantity of nano zirconia is that of the precursor and Li (OH)2500ppm of the total mass;
(II) placing the materials after primary mixing in an oxygen atmosphere (the oxygen concentration is more than or equal to 99.99%) with the oxygen flow of 5L/min, heating to 800 ℃ at the heating rate of 2 ℃/min, preserving the heat for 15h, and sieving the sintered materials;
(III) secondarily mixing the sintering material and boric acid according to the mass ratio of 1:0.3 for 10min, then placing in a nitrogen atmosphere, heating to 300 ℃ at the heating rate of 2 ℃/min, preserving heat for 20h, and sieving to obtain the single crystal nickel cobalt lithium manganate positive electrode material.
Comparative example 4
The embodiment provides an interface composite modification method of a nickel cobalt lithium manganate positive electrode material, which specifically comprises the following steps:
(I) precursor Ni0.8Co0.1Mn0.1(OH)2、Li(OH)2Mixing with nanometer zirconia for 10min in one time, Li (OH)2And the precursor is fed according to the mol ratio of Li (Ni + Co + Mn) ═ 1, the adding quantity of nano zirconia is that of the precursor and Li (OH)2500ppm of the total mass;
and (II) placing the material subjected to primary mixing in an oxygen atmosphere with oxygen flow of 5L/min (oxygen concentration is more than or equal to 99.99%), heating to 800 ℃ at the heating rate of 2 ℃/min, preserving heat for 15h, and sieving to obtain the single crystal nickel cobalt lithium manganate positive electrode material.
The lithium nickel cobalt manganese oxide single-crystal positive electrode materials prepared in examples 1-12 and comparative examples 1-4 were mixed with a conductive agent, a binder and NMP, and after uniform mixing, the lithium nickel cobalt manganese oxide single-crystal positive electrode materials were coated, rolled, and cut into pieces in sequence, and button cells were assembled, so that the electrochemical performance of the positive electrode materials was evaluated, and the electrochemical test results are shown in table 1, and the 50-cycle curve of the single-crystal lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 is shown in fig. 2.
TABLE 1
As can be seen from the data in table 1:
(1) compared with comparative examples 1 to 4, the positive electrode materials prepared in examples 1 to 14 have higher charge-discharge capacity at 0.1C, higher first-discharge coulombic efficiency and higher rate performance than those of comparative examples 1 to 4;
(2) in example 1, compared with examples 7-10, the dosage of cyanuric acid in example 7 is too high, while the dosage of cyanuric acid in example 8 is too low, and the electrochemical performance of the material is affected by the too high or too low dosage of cyanuric acid, because the cyanuric acid has influence on the particle size and the interface stability; similarly, the feeding amount of the boric acid in example 9 is too high, while the feeding amount of the boric acid in example 10 is too low, and the electrochemical performance of the material is affected by too high or too low feeding amount of the boric acid; this is because the boron coating thickness affects lithium ion deintercalation;
(3) compared with the comparative example 1, the step (I) of the comparative example 1 does not add the nano zirconia, so that the electrochemical performance of the material is reduced, and the structural stability is deteriorated in the circulating process;
(4) compared with the comparative example 2, the step (III) of the comparative example 2 is not added with boric acid, so that the electrochemical performance of the material is reduced, because no boric acid is involved, cyanuric acid can not form a coating layer, and the reaction of the positive electrode and the electrolyte is inhibited;
(5) compared with the comparative example 3, in the step (iii) of the comparative example 1, cyanuric acid is not added, so that the electrochemical performance of the material is reduced, because the boron nitride structure formed by boric acid and cyanuric acid is more stable, and the side reaction of the material and the electrolyte can be inhibited;
(6) in comparison with example 1 and comparative example 4, cyanuric acid and boric acid were not added in step (iii) of comparative example 1, resulting in a decrease in electrochemical properties of the material due to severe side reactions with the electrolyte without coating by the coating layer.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The interface composite modification method of the cathode material is characterized by comprising the following steps:
and the precursor, the lithium source and the nano oxide are mixed for the first time and then calcined to obtain a sintering material, and the sintering material, the inducer and the boron source are mixed for the second time and then calcined to obtain the single crystal anode material.
2. The method for interfacial composite modification according to claim 1, wherein the precursor has a chemical formula of NixCoyMnz(OH)2，x≥0.8，x+y+z＝1，0＜y，z＜1；
Preferably, the lithium source and the precursor are mixed according to the molar ratio of Li (Ni + Co + Mn) being 1-1.15;
preferably, the adding amount of the nano oxide is 500-3000 ppm of the total mass of the precursor and the lithium source;
preferably, the nano-oxide comprises any one or a combination of at least two of zirconium oxide, titanium oxide, tungsten oxide, molybdenum oxide, aluminum oxide or yttrium oxide;
preferably, the time of the primary mixing is 10-30 min.
3. The interfacial composite modification method according to claim 1 or 2, wherein the calcination process is performed under an oxygen atmosphere;
preferably, the oxygen flow of the oxygen atmosphere is 5-20L/min;
preferably, the oxygen concentration of the oxygen atmosphere is more than or equal to 99.99%.
4. The interface composite modification method according to any one of claims 1 to 3, wherein the temperature rise rate of the calcination is 2 to 5 ℃/min;
preferably, the calcining temperature is 800-950 ℃;
preferably, the calcining heat preservation time is 5-15 h;
preferably, the sintered material is obtained by sieving the product after calcination.
5. The interfacial composite modification method according to any one of claims 1 to 4, wherein the mass ratio of the sintering material, the inducer and the boron source is 1 (0.2-1.0) to (0.1-0.5);
preferably, the inducer comprises cyanuric acid, dicyandiamide, hydroxyethyl urea or melamine;
preferably, the boron source comprises boric acid and/or boron oxide;
preferably, the time of the secondary mixing is 10-30 min.
6. The method for interfacial composite modification according to any one of claims 1 to 5, wherein the firing process is performed under a protective atmosphere;
preferably, the protective atmosphere comprises a nitrogen atmosphere or an argon atmosphere;
preferably, the temperature rise rate in the roasting process is 2-5 ℃/min;
preferably, the roasting temperature is 300-700 ℃;
preferably, the roasting heat preservation time is 4-20 h.
7. The interfacial composite modification method according to any one of claims 1 to 6, wherein the interfacial composite modification method comprises the steps of:
(I) precursor NixCoyMnz(OH)2Mixing the lithium source and the nano oxide for 10-30 min at one time, feeding the lithium source and the precursor according to the molar ratio of Li (Ni + Co + Mn) being 1-1.15, wherein the addition amount of the nano oxide is 500-3000 ppm of the total mass of the precursor and the lithium source;
(II) placing the materials after primary mixing in an oxygen atmosphere with the oxygen flow of 5-20L/min, heating to 800-950 ℃ at the heating rate of 2-5 ℃/min, preserving heat for 5-15 h, and sieving to sinter the materials;
and (III) secondarily mixing the sintering material, the inducer and the boron source according to the mass ratio of 1 (0.2-1.0) to (0.1-0.5) for 10-30 min, then placing in a protective atmosphere, raising the temperature to 300-700 ℃ at the temperature rise rate of 2-5 ℃/min, preserving the temperature for 4-20 h, and sieving to obtain the single crystal anode material.
8. A positive electrode material prepared by the interfacial composite modification method of any one of claims 1 to 7.
9. The positive electrode material according to claim 8, wherein the particle size D50 of the positive electrode material is 3 to 4 μm;
preferably, the specific surface area of the positive electrode material is 0.5-0.8 m2/g；
Preferably, the pH value of the positive electrode material is less than or equal to 11.8;
preferably, the surface residual alkali of the cathode material is less than or equal to 3500 ppm.
10. A lithium battery comprising a positive electrode, a separator and a negative electrode stacked in this order, the positive electrode comprising the positive electrode material as claimed in claim 8 or 9.
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