CN114031124B - Tungsten double-coated positive electrode material and preparation method and application thereof - Google Patents

Tungsten double-coated positive electrode material and preparation method and application thereof Download PDF

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CN114031124B
CN114031124B CN202111289834.5A CN202111289834A CN114031124B CN 114031124 B CN114031124 B CN 114031124B CN 202111289834 A CN202111289834 A CN 202111289834A CN 114031124 B CN114031124 B CN 114031124B
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tungsten
positive electrode
electrode material
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double
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CN114031124A (en
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莫方杰
朱呈岭
李岚
杨元婴
杨文龙
孙化雨
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • C01—INORGANIC CHEMISTRY
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    • C01P2006/40—Electric properties
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Abstract

The invention provides a tungsten double-coated positive electrode material, a preparation method and application thereof, wherein the tungsten double-coated positive electrode material comprises a positive electrode material, a first tungsten compound and a second tungsten compound; the chemical formula of the positive electrode material is LiNi x Co y Mn 1‑x‑y O 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13; the first tungsten compound and the second tungsten compound are different tungsten compounds; the first tungsten compound and the second tungsten compound are coated on the surface of the positive electrode material; according to the invention, two different tungsten compounds are coated on the surface of the low-cobalt positive electrode material to prepare the tungsten double-coated positive electrode material, so that the conductivity of the surface of the material is effectively improved; the method is used for preparing the positive pole piece of the lithium ion battery, can reduce the internal resistance of the battery and improve the capacity retention rate of the battery under the low-temperature condition.

Description

Tungsten double-coated positive electrode material and preparation method and application thereof
Technical Field
The invention belongs to the field of battery material preparation, and particularly relates to a tungsten double-coated positive electrode material, and a preparation method and application thereof.
Background
Ternary cathode material LiNi x Co y Mn 1-x-y O 2 The catalyst has higher theoretical specific capacity, higher reaction platform voltage and excellent reaction kinetics, so that the catalyst is widely applied to a power battery system with high energy density, the theoretical specific capacity reaches 274mAh/g, and the reaction platform voltage is 3.0V to 4.3V. However, the ternary positive electrode material widely used at present has higher cobalt content and LiNi x Co y Mn 1-x-y O 2 In which y is greater than 0.15, cobalt ore is increasingly in demand as a rare mineral resource.
In the prior art, the content of cobalt in the ternary positive electrode material is reduced to solve the problems of material cost and limited cobalt ore resources, and the low-cobalt positive electrode material LiNi is developed x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13.
The reduction of the cobalt content in the low-cobalt positive electrode material can reduce the overall conductivity of the material and improve the diffusion barrier of lithium ions in crystal lattices, so that serious reaction kinetics retardation problem is brought, and the capacity exertion of a battery is influenced. Particularly, under the low temperature condition that the temperature is less than minus 20 ℃, the direct current internal resistance and the capacity retention rate of the composite material are obviously deteriorated. This can lead to a decrease in the energy density of the low cobalt cathode material, affecting the development and application of the material.
Therefore, there is a need to develop a positive electrode material having a high energy density under low temperature conditions.
Disclosure of Invention
The invention aims to provide a tungsten double-coated positive electrode material, a preparation method and application thereof, wherein the tungsten double-coated positive electrode materialThe electrode material comprises a positive electrode material, a first tungsten compound and a second tungsten compound; the chemical formula of the positive electrode material is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13; the first tungsten compound and the second tungsten compound are different tungsten compounds; the first tungsten compound and the second tungsten compound are coated on the surface of the positive electrode material; according to the invention, two different tungsten compounds are coated on the surface of the low-cobalt positive electrode material to prepare the tungsten double-coated positive electrode material, so that the conductivity of the surface of the material is effectively improved; the method is used for preparing the positive pole piece of the lithium ion battery, can reduce the internal resistance of the battery and improve the capacity retention rate of the battery under the low-temperature condition.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide a tungsten double-coated positive electrode material comprising a positive electrode material, a first tungsten compound and a second tungsten compound; wherein:
the chemical formula of the positive electrode material is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13;
the first tungsten compound and the second tungsten compound are different tungsten compounds;
the first tungsten compound and the second tungsten compound are coated on the surface of the positive electrode material.
According to the invention, two different tungsten compounds are coated on the surface of the positive electrode material to improve the conductivity of the surface of the positive electrode material, the first tungsten compound is a tungsten source with high activity, so that the first tungsten compound is firmly combined with the surface of the positive electrode material, and the second tungsten compound is a tungsten source with good crystallinity, so that the conductivity of the positive electrode material is further improved, and the energy density of a positive electrode plate prepared by using the first tungsten compound is higher.
It should be noted that the chemical coefficient of Co in the positive electrode material may be 0, that is, y=0, which means that the positive electrode material coated with the tungsten compound may not contain Co.
As a preferable embodiment of the present invention, the first tungsten compound is distributed in a planar shape.
Preferably, the crystal form of the first tungsten compound is an amorphous form.
Preferably, the second tungsten compound is punctiform in distribution.
Preferably, the crystal form of the second tungsten compound is in a crystalline state.
In a preferred embodiment of the present invention, the positive electrode material is in a secondary spherical form and/or a single crystal form.
Preferably, the D50 particle size of the secondary sphere form is 9 μm to 25. Mu.m, for example, 9 μm,10 μm,11 μm,12 μm,13 μm,14 μm,15 μm,16 μm,17 μm,18 μm,19 μm,20 μm,21 μm,22 μm,23 μm,24 μm,25 μm, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable.
The D50 particle size of the single crystal form is preferably 2 μm to 6 μm, and may be, for example, 2 μm,2.5 μm,3 μm,3.5 μm,4 μm,4.5 μm,5 μm,5.5 μm,6 μm, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Another object of the present invention is to provide a method for preparing the tungsten double-coated positive electrode material, which comprises the steps of:
sintering the anode material and a first tungsten source for one time at the temperature of 500-700 ℃ to obtain a tungsten single-coated anode material;
and carrying out secondary sintering on the tungsten single-coated anode material and a second tungsten source at the temperature of 300-500 ℃ to obtain the tungsten double-coated anode material.
According to the invention, two tungsten compounds are coated on the surface of the positive electrode plate through twice sintering, so that the preparation method is simple and convenient, and the operation is easy.
It should be noted that, when the positive electrode material does not contain Co, the corresponding preparation method needs to omit the cobalt source.
The preferred primary sintering temperature of the present invention is 500 to 700 ℃, for example, 500, 520, 540, 560, 580, 600, 620, 640, 660, 680, 700, etc., but not limited to the values recited, and other values not recited in the range are equally applicable; if the temperature is higher than 700 ℃, the volatilization of a lithium source is serious, and the gram capacity of the material is reduced; if the temperature is lower than 500 ℃, the phase inversion is insufficient, and a pure-phase positive electrode material cannot be obtained.
The temperature of the secondary sintering is preferably 300 ℃ to 500 ℃, and can be 300 ℃,320 ℃,340 ℃,360 ℃,380 ℃,400 ℃,420 ℃,440 ℃,460 ℃,480 ℃,500 ℃ and the like, for example, but the secondary sintering is not limited to the listed values, and other non-listed values in the range of the values are equally applicable; if the temperature is higher than 500 ℃, the volatilization of a lithium source is serious, and the gram capacity of the material is reduced; if the temperature is lower than 300 ℃, the coating effect is poor, the adhesive force of the coating agent is low, and the coating agent is easy to fall off.
As a preferred embodiment of the present invention, the first tungsten source includes H 2 W 2 O 7 、WO 3 Or WO 2 Any one or a combination of at least two, examples of which include H 2 W 2 O 7 And WO 3 Is a combination of H 2 W 2 O 7 And WO 2 Is a combination of WO 3 And WO 2 More preferably H 2 W 2 O 7 。
Preferably, the time for the primary sintering is 10h to 25h, and may be, for example, 10h,11h,12h,13h,14h,15h,16h,17h,18h,19h,20h,21h,22h,23h,24h,25h, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the second tungsten source comprises BW and B 2 W、W 2 N 3 、WF 6 、WF 4 Or WOF 4 Any one or a combination of at least two, examples of which include BW and B 2 Combinations of W, B 2 W and W 2 N 3 Is a combination of B 2 W and WF 6 W and WF of the combination of BW and WF 6 Combination, W 2 N 3 And WF 6 Is a combination of WF 6 And WF 4 Is a combination of WF 6 And WOF 4 Is a combination of B 2 W and WF 4 Is a combination of WF 4 And WOF 4 BW and WOF 4 Further preferably WF 6 ；
Preferably, the secondary sintering time is 5h to 10h, for example, 5h,6h,7h,8h,9h,10h, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
In a preferred embodiment of the present invention, the ratio of the total mass of the first tungsten source to the second tungsten source is 0.01% to 2%, for example, 0.01%,0.05%,0.08%,0.1%,0.2%,0.3%,0.4%,0.5%,0.6%,0.7%,0.8%,0.9%,1%,1.1%,1.2%,1.3%,1.4%,1.5%,1.6%,1.7%,1.8%,1.9%,2%, etc., and more preferably 1.2% to 1.4%, for example, 1.2%,1.22%,1.25%,1.28%,1.3%,1.33%,1.35%,1.37%,1.4%, etc., but the ratio is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the mass of the first tungsten source accounts for 10% to 30% of the sum of the masses of the first tungsten source and the second tungsten source, and may be, for example, 10%,11%,12%,13%,14%,15%,16%,17%,18%,19%,20%,21%,22%,23%,24%,25%,26%,27%,28%,29%,30%, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
the anode material and a first tungsten source are subjected to primary sintering at the temperature of 500-700 ℃ for 10-25 hours, so that a tungsten single-coated anode material is obtained;
carrying out secondary sintering on the tungsten single-coated anode material and a second tungsten source at the temperature of 300-500 ℃ for 5-10 hours to obtain a tungsten double-coated anode material;
wherein the first tungsten source comprises H 2 W 2 O 7 、WO 3 Or WO 2 Any one or a combination of at least two of the following; the second tungsten source comprises BW, B 2 W、W 2 N 3 、WF 6 、WF 4 Or WOF 4 Any one or a combination of at least two of the following; the sum of the masses of the first tungsten source and the second tungsten source accounts for 0.01 to 2 percent of the total feeding amount; the mass of the first tungsten source accounts for 10-30% of the sum of the masses of the first tungsten source and the second tungsten source.
The invention further aims to provide an application of the tungsten double-coated positive electrode material for preparing a positive electrode plate of a lithium ion battery.
A fourth object of the present invention is to provide a method for applying the tungsten double-coated positive electrode material according to the third object, the method comprising:
mixing conductive carbon black, conductive carbon tubes, a nitrogen methyl pyrrolidone solvent and polyvinylidene fluoride, and dispersing and stirring at a high speed for 2 hours to obtain conductive slurry; mixing a tungsten double-coated anode material with the conductive slurry to obtain anode slurry; uniformly coating the positive electrode slurry on an aluminum foil by using a scraper, placing the aluminum foil in a blast drying oven, drying at 120 ℃ for 20 minutes, and rolling and cutting to prepare a positive electrode plate;
wherein the mass ratio of the tungsten double-coated positive electrode material to the conductive carbon black to the conductive carbon tube to the nitrogen methyl pyrrolidone solvent to the polyvinylidene fluoride is (90-99) 1:0.5:40:1.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the tungsten double-coated anode material is prepared by coating two different tungsten compounds on the surface of the low-cobalt anode material, so that the conductivity of the surface of the material is effectively improved, and the diffusion of lithium ions is promoted; the method is used for preparing the positive pole piece of the lithium ion battery, can effectively reduce the direct current resistance of the battery, reduce the low-temperature direct current resistance of the battery and improve the capacity retention rate of the battery under the low-temperature condition.
Drawings
FIG. 1 shows the DC resistance values of the positive electrode sheets obtained in example 1 and comparative examples 1 and 2 at 25deg.C under different charge states;
FIG. 2 shows the DC resistance values of the positive electrode sheets obtained in example 1 and comparative examples 1 and 2 at-20deg.C and different charge states;
fig. 3 shows the battery capacity retention at-20 ℃ of the positive electrode sheets obtained in example 1 and comparative examples 1 and 2.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the prior art, a technical scheme provides a tungsten-titanium co-coated lithium ion ternary cathode material and a preparation method thereof, wherein the method comprises the following steps: dissolving a tungsten source compound, a titanium source compound and a stabilizer in a solvent to form a blend; adding a proper amount of lithium battery ternary material into the blending liquid, and uniformly stirring to obtain slurry; spraying high-pressure lithium source water mist into the slurry, stirring, removing solvent, and drying to obtain a mixed material; calcining the mixed material, cooling to obtain a tungsten-titanium co-coated lithium ion ternary positive electrode material, wherein the inner core of the material is a lithium battery ternary material, and the outer layer of the material is a continuous and uniform tungsten-titanium composite film; according to the technical scheme, tungsten and titanium inorganic salts are slowly decomposed in an alcohol phase, and a tungsten-titanium composite oxide film is formed on the surface of a finished ternary material, so that the surface modification film is beneficial to improving the cycle performance of the positive electrode material at high temperature, and reaction byproducts are beneficial to improving the processing performance of the positive electrode material.
Another proposal provides a ternary positive electrode material with a surface layer coated with lithium tungstate and doped with W and a preparation method thereof. The preparation of the precursor in the method adopts the current industrialized coprecipitation method of hydrogen oxide, and the method is simple and convenient, low in production cost and mild in process condition. According to the technical scheme, the preparation of the ternary positive electrode material with the surface layer coated with the lithium tungstate and doped with W is realized by a one-step method, namely, a tungsten source is added in the process of mixing a precursor and lithium salt, and the ternary positive electrode material is obtained by high-temperature calcination, so that the preparation method is simple. The surface layer is coated with lithium tungstate and the W-doped ternary positive electrode material can solve the problems of poor overall cycling performance and the like of the high-nickel ternary positive electrode material caused by unstable surface layer structure in the cycling process, and the electrochemical performance and the structural stability of the ternary positive electrode material are improved by utilizing the synergistic effect of the coating and the doping, so that the high-performance high-nickel ternary positive electrode material is obtained.
However, the preparation steps of the technical scheme are complicated, and the preparation steps are all aimed at modification of the ternary anode material with the conventional cobalt content, when the cobalt content is low, the overall conductivity of the material is reduced, the diffusion barrier of lithium ions in crystal lattices is improved, so that the serious reaction kinetics hysteresis problem is brought, the capacity exertion of a battery is influenced, and particularly, the direct current internal resistance and the capacity retention rate are obviously reduced under the low-temperature condition below-20 ℃; the above technical solution does not prove whether it can be applied to a low cobalt cathode material.
According to the embodiment of the disclosure, through twice sintering, the surface of the low-cobalt positive electrode material with the cobalt content less than 0.13 is coated with two tungsten compounds with different forms and different crystal forms, so that the ion and electron conductivity of the surface of the material can be effectively improved, the internal resistance of the battery is reduced, and the low-temperature performance is improved.
Example 1
The embodiment provides a tungsten double-coated positive electrode material and a positive electrode plate prepared by using the same, and the preparation method comprises the following steps:
the anode material LiNi 0.66 Co 0.11 Mn 0.23 O 2 And H is 2 W 2 O 7 Sintering at 600 deg.c for 18 hr to obtain single tungsten coated anode material and WF 6 Secondary sintering is carried out for 8 hours at 400 ℃ to obtain a tungsten double-coated anode material; wherein the H is 2 W 2 O 7 And WF (WF) 6 The mass sum accounts for 1.1 percent of the total feeding amount; the H is 2 W 2 O 7 Is H in mass 2 W 2 O 7 And WF (WF) 6 20% of the sum of the masses;
mixing conductive carbon black, conductive carbon tubes, a nitrogen methyl pyrrolidone solvent and polyvinylidene fluoride, and dispersing and stirring at a high speed for 2 hours to obtain conductive slurry; mixing a tungsten double-coated anode material with the conductive slurry to obtain anode slurry; uniformly coating the positive electrode slurry on an aluminum foil by using a scraper, placing the aluminum foil in a blast drying oven, drying at 120 ℃ for 20 minutes, and rolling and cutting to prepare a positive electrode plate; wherein the mass ratio of the tungsten double-coated anode material to the conductive carbon black to the conductive carbon tube to the nitrogen methyl pyrrolidone solvent to the polyvinylidene fluoride is 97.5:1:0.5:40:1.
Example 2
The embodiment provides a tungsten double-coated positive electrode material and a positive electrode plate prepared by using the same, and the preparation method comprises the following steps:
the anode material LiNi 0.9 Mn 0.1 O 2 And H is 2 W 2 O 7 Sintering at 700 deg.c for 10 hr to obtain single tungsten coated anode material and B 2 Sintering the tungsten for 5 hours at 500 ℃ to obtain a tungsten double-coated anode material; wherein the H is 2 W 2 O 7 And B is connected with 2 The sum of the W masses accounts for 2% of the total feeding amount; the H is 2 W 2 O 7 Is H in mass 2 W 2 O 7 And B is connected with 2 10% of the sum of W masses;
mixing conductive carbon black, conductive carbon tubes, a nitrogen methyl pyrrolidone solvent and polyvinylidene fluoride, and dispersing and stirring at a high speed for 2 hours to obtain conductive slurry; mixing a tungsten double-coated anode material with the conductive slurry to obtain anode slurry; uniformly coating the positive electrode slurry on an aluminum foil by using a scraper, placing the aluminum foil in a blast drying oven, drying at 120 ℃ for 20 minutes, and rolling and cutting to prepare a positive electrode plate; wherein the mass ratio of the tungsten double-coated anode material to the conductive carbon black to the conductive carbon tube to the nitrogen methyl pyrrolidone solvent to the polyvinylidene fluoride is 99:1:0.5:40:1.
Comparative example 1
This comparative example provides oneThe positive electrode material and the positive electrode sheet prepared by using the same are different from each other only in that, with reference to example 1: omit H 2 W 2 O 7 And WF 6 Namely, the preparation method comprises the following steps:
mixing conductive carbon black, conductive carbon tubes, a nitrogen methyl pyrrolidone solvent and polyvinylidene fluoride, and dispersing and stirring at a high speed for 2 hours to obtain conductive slurry; the anode material LiNi 0.66 Co 0.11 Mn 0.23 O 2 Mixing the positive electrode slurry with the conductive slurry to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil by using a scraper, placing the aluminum foil in a blast drying oven, drying at 120 ℃ for 20 minutes, and rolling and cutting to prepare a positive electrode plate; wherein the mass ratio of the positive electrode material to the conductive carbon black to the conductive carbon tube to the nitrogen methyl pyrrolidone solvent to the polyvinylidene fluoride is 97.5:1:0.5:40:1.
Comparative example 2
This comparative example provides a tungsten single-coated positive electrode material and a positive electrode sheet prepared by using the same, and the preparation method is different from that of example 1 only in that: omitting WF 6 Namely, the preparation method comprises the following steps:
the anode material LiNi 0.66 Co 0.11 Mn 0.23 O 2 And H is 2 W 2 O 7 Sintering for 18 hours at 600 ℃ once to obtain a tungsten single-coated anode material; wherein the H is 2 W 2 O 7 The mass ratio of the catalyst to the total feeding amount is 1.1 percent;
mixing conductive carbon black, conductive carbon tubes, a nitrogen methyl pyrrolidone solvent and polyvinylidene fluoride, and dispersing and stirring at a high speed for 2 hours to obtain conductive slurry; mixing a tungsten single-coated positive electrode material with the conductive slurry to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil by using a scraper, placing the aluminum foil in a blast drying oven, drying at 120 ℃ for 20 minutes, and rolling and cutting to prepare a positive electrode plate; wherein the mass ratio of the tungsten single-coated positive electrode material to the conductive carbon black to the conductive carbon tube to the nitrogen methyl pyrrolidone solvent to the polyvinylidene fluoride is 97.5:1:0.5:40:1.
Comparative example 3
This comparative example provides a tungsten double-coated positive electrode material and a positive electrode sheet prepared using the same, except that the temperature of the primary sintering was changed from 600 ℃ to 750 ℃, and the other conditions were exactly the same as in example 1.
Comparative example 4
This comparative example provides a tungsten double-coated positive electrode material and a positive electrode sheet prepared using the same, and the other conditions were exactly the same as in example 1 except that the temperature of the primary sintering was changed from 600 to 450 ℃.
Comparative example 5
This comparative example provides a tungsten double-coated positive electrode material and a positive electrode sheet prepared using the same, except that the temperature of the secondary sintering was changed from 400 ℃ to 550 ℃, and the other conditions were exactly the same as in example 1.
Comparative example 6
This comparative example provides a tungsten double-coated positive electrode material and a positive electrode sheet prepared using the same, except that the temperature of the secondary sintering was changed from 400 ℃ to 250 ℃, and the other conditions were exactly the same as in example 1.
The positive electrode sheets obtained in the above examples and comparative examples were tested for DC resistance at 25℃and DC resistance at-20℃and battery capacity retention at-20℃with the charge state maintained at 50% SOC, as follows:
dc resistance value at 25 ℃): charging to 4.3V voltage at 25deg.C rate of 0.33C, discharging to 2.8V at 0.33C rate to obtain battery capacity C 0 The method comprises the steps of carrying out a first treatment on the surface of the Then the state of charge of the battery is adjusted to 50% SOC, then the battery is discharged for 30s at the current density of 4C, and the voltage difference value before and after the discharge is divided by the current density, namely the direct current resistance value of the battery in the state of charge; the direct current resistance values of 70% SOC and 20% SOC at 25 ℃ can be obtained by the method;
-low temperature dc resistance value at-20 ℃): charging to 4.3V voltage at-20deg.C rate of 0.33C, discharging to 2.8V at 0.33C rate to obtain battery capacity C 1 The method comprises the steps of carrying out a first treatment on the surface of the Then the state of charge of the battery is adjusted to 50% SOC, then the battery is discharged for 30s at the current density of 4C, and the voltage difference value before and after the discharge is divided by the current density, namely the direct current resistance value of the battery in the state of charge; the direct current resistance values of 70% SOC and 20% SOC at-20 ℃ can be obtained by the method;
battery capacity retention at-20 ℃ of C 1 /C 0 X 100%, where C 0 A battery capacity of 25 ℃; c (C) 1 Is a battery capacity of-20 ℃.
The test results of the above examples and comparative examples are shown in Table 1.
TABLE 1
From table 1, the following points can be found:
(1) Comparing example 1 with comparative examples 1 and 2, it was found that H was omitted due to comparative example 1 2 W 2 O 7 And WF 6 The surface conductivity of the positive electrode material is reduced, so that when the charge state is 50% SOC, the direct current resistance values at 25 ℃ and-20 ℃ are obviously increased, and the capacity retention rate of the battery at-20 ℃ is reduced; WF was omitted due to comparative example 2 6 Only the surface of the positive electrode material is coated with H 2 W 2 O 7 This resulted in the tungsten single-coated positive electrode material surface obtained in comparative example 2 having a tungsten compound content greater than that of the positive electrode material obtained in comparative example 1 and less than that of the tungsten double-coated positive electrode material obtained in example 1, thereby rendering the positive electrode material surface inferior in conductivity to example 1 and superior to that of comparative example 1, and further resulted in direct current resistance values of 25 ℃ and-20 ℃ being between example 1 and comparative example 1 and battery capacity retention of-20 ℃ being also between example 1 and comparative example 1 when the state of charge is 50% soc;
(2) Comparing example 1 with comparative examples 3 to 6, it was found that since the temperature of primary sintering in comparative example 3 is 750℃and exceeds the preferred 500℃to 700℃of the present invention, the volatilization of lithium source is serious, the gram capacity of the material is reduced, the content of lithium element in the structural formula of the positive electrode material is reduced, and the chemical formula becomes Li 0.9 Ni 0.66 Co 0.11 Mn 0.23 O 2 Further, when the charge state is 50% SOC, the direct current resistance values at 25 ℃ and-20 ℃ are increased, and the battery capacity retention rate at-20 ℃ is reduced; since the temperature of the primary sintering in comparative example 4 was 450℃lower than the preferred 5 of the present inventionThe phase inversion is insufficient at the temperature of 00 ℃ to 700 ℃, a pure-phase positive electrode material cannot be obtained, a first tungsten source cannot be successfully coated on the surface of the positive electrode material, namely, a tungsten double-coated positive electrode material is free of a first tungsten compound, so that when the charge state is 50% SOC, the direct current resistance values at 25 ℃ and-20 ℃ are increased, and the capacity retention rate of a battery at-20 ℃ is reduced; since the temperature of the secondary sintering in comparative example 5 is 550 ℃ and exceeds the preferable 300 ℃ to 500 ℃ of the invention, the volatilization of the lithium source is serious, the gram capacity of the material is reduced, the content of lithium element in the structural formula of the positive electrode material is reduced, and the chemical formula of the positive electrode material is changed into Li 0.98 Ni 0.66 Co 0.11 Mn 0.23 O 2 Further, the DC resistance value is increased, and the battery capacity retention rate at-20 ℃ is reduced; because the temperature of the secondary sintering of comparative example 6 is 250 ℃ and lower than the preferable 300 ℃ to 500 ℃ of the invention, the coating effect is poor, the second tungsten source cannot be successfully coated on the surface of the positive electrode material, namely, the tungsten double-coated positive electrode material is free of a second tungsten compound, and the direct current resistance value is increased, and the capacity retention rate of the battery at minus 20 ℃ is reduced;
(2) Comparing comparative examples 1 and 2 with comparative examples 3 to 6, it was found that the dc resistance values at 25 ℃ and-20 ℃ of comparative example 3 and comparative example 5 are higher than those of comparative example 1 and comparative example 2, because the temperature of the primary sintering in comparative example 3 is too high and the temperature of the secondary sintering in comparative example 5 is too high, the volatilization of the lithium source is serious due to the too high temperature during sintering, the structural formula of the positive electrode material is changed, the smaller particles in the positive electrode material are aggregated into large particles, and the structure of the positive electrode material itself is changed, so that the dc resistance value is higher than that of comparative example 1 and comparative example 2; the dc resistance values of comparative example 4 and comparative example 6 were higher than those of comparative example 2 at 25 c and-20 c, because the temperature of the primary sintering in comparative example 4 was too low and the temperature of the secondary sintering in comparative example 6 was too low, the tungsten double-coated positive electrode material obtained in comparative example 4 was free of the first tungsten compound, the tungsten double-coated positive electrode material obtained in comparative example 6 was free of the second tungsten compound, and the conductivity of the surface of the positive electrode material was deteriorated, and the dc resistance value was increased.
To further verify the dc resistance values at 25 c, the dc resistance values at-20 c and the battery capacity retention rates at-20 c at different charge states, tests were performed by taking example 1 and comparative examples 1 and 2 as examples, the dc resistance values at 25 c of the positive electrode sheets obtained in example 1 and comparative examples 1 and 2 are shown in fig. 1, the dc resistance values at-20 c of the positive electrode sheets obtained in example 1 and comparative examples 1 and 2 are shown in fig. 2, and the capacity retention rates at-20 c of the positive electrode sheets obtained in example 1 and comparative examples 1 and 2 are shown in fig. 3, and specific values of fig. 1 to 3 are shown in table 2.
TABLE 2
From fig. 1-3 and table 2, it can be derived that:
the positive electrode plate described in example 1 has the lowest direct current resistance value at different charge states and different temperatures, and the highest battery capacity retention rate at-20 ℃; the positive electrode plate in comparative example 1 has the highest direct current resistance value at different charge states and different temperatures, and the battery capacity retention rate at-20 ℃ is lowest; the positive electrode sheet described in comparative example 2 had both direct current resistance values at different charge states and different temperatures and a battery capacity retention rate of-20 ℃ between example 1 and comparative example 1.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (16)

1. The tungsten double-coated positive electrode material is characterized by comprising a positive electrode material core, a first tungsten compound coating layer and a second tungsten compound coating layer from inside to outside, wherein:
the positive directionThe chemical formula of the electrode material core is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13;
the first tungsten compound is distributed in a plane shape; the crystal form of the second tungsten compound is in a crystalline state;
the first tungsten compound coating layer is obtained from a first tungsten source;
the second tungsten compound coating is obtained from a second tungsten source;
the first tungsten source comprises H 2 W 2 O 7 、WO 3 Or WO 2 Any one or a combination of at least two of the following;
the second tungsten source comprises BW, B 2 W、W 2 N 3 、WF 6 、WF 4 Or WOF 4 Any one or a combination of at least two of these.
2. The tungsten double-coated positive electrode material according to claim 1, wherein the crystal form of the first tungsten compound is an amorphous form.
3. The tungsten double-coated positive electrode material according to claim 1, wherein the second tungsten compound is distributed in a dot shape.
4. The tungsten double-coated positive electrode material according to claim 1, wherein the positive electrode material is in a secondary sphere form and/or a single crystal form.
5. The tungsten double-coated positive electrode material according to claim 4, wherein the D50 particle diameter of the secondary sphere form is 9 μm to 25 μm.
6. The tungsten double-coated positive electrode material according to claim 4, wherein the D50 particle diameter of the single crystal form is 2 μm to 6 μm.
7. A method for producing a tungsten double-coated positive electrode material according to any one of claims 1 to 6, characterized in that the method comprises:
sintering the anode material and a first tungsten source for one time at the temperature of 500-700 ℃ to obtain a tungsten single-coated anode material;
carrying out secondary sintering on the tungsten single-coated anode material and a second tungsten source at the temperature of 300-500 ℃ to obtain a tungsten double-coated anode material;
the first tungsten source comprises H 2 W 2 O 7 、WO 3 Or WO 2 Any one or a combination of at least two of the following;
the second tungsten source comprises BW, B 2 W、W 2 N 3 、WF 6 、WF 4 Or WOF 4 Any one or a combination of at least two of these.
8. The method for preparing a tungsten double-coated positive electrode material according to claim 7, wherein the first tungsten source is H 2 W 2 O 7 。
9. The method for producing a tungsten double-coated positive electrode material according to claim 7, wherein the time for the primary sintering is 10 hours to 25 hours.
10. The method for preparing a tungsten double-coated positive electrode material according to claim 7, wherein the second tungsten source is WF 6 。
11. The method for producing a tungsten double-coated positive electrode material according to claim 7, wherein the time for the secondary sintering is 5 hours to 10 hours.
12. The method for producing a tungsten double-coated positive electrode material according to claim 7, wherein the ratio of the sum of the masses of the first tungsten source and the second tungsten source to the total feed amount is 0.01% to 2%.
13. The method for producing a tungsten double-coated positive electrode material according to claim 12, wherein the ratio of the sum of the masses of the first tungsten source and the second tungsten source to the total feed amount is 1.2% to 1.4%.
14. The method of producing a tungsten double-coated cathode material according to claim 7, wherein the mass of the first tungsten source is 10% to 30% of the sum of the masses of the first tungsten source and the second tungsten source.
15. The method for producing a tungsten double-coated positive electrode material according to any one of claim 7, comprising:
the anode material and a first tungsten source are subjected to primary sintering at the temperature of 500-700 ℃ for 10-25 hours, so that a tungsten single-coated anode material is obtained;
carrying out secondary sintering on the tungsten single-coated anode material and a second tungsten source at the temperature of 300-500 ℃ for 5-10 hours to obtain a tungsten double-coated anode material;
wherein the first tungsten source comprises H 2 W 2 O 7 、WO 3 Or WO 2 Any one or a combination of at least two of the following; the second tungsten source comprises BW, B 2 W、W 2 N 3 、WF 6 、WF 4 Or WOF 4 Any one or a combination of at least two of the following; the sum of the masses of the first tungsten source and the second tungsten source accounts for 0.01 to 2 percent of the total feeding amount; the mass of the first tungsten source accounts for 10-30% of the sum of the masses of the first tungsten source and the second tungsten source.
16. Use of a tungsten double-coated positive electrode material according to any one of claims 1 to 6 for the preparation of a positive electrode sheet of a lithium ion battery.
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