CN113451582B - Tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material and preparation method thereof - Google Patents

Tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material and preparation method thereof Download PDF

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CN113451582B
CN113451582B CN202111000494.XA CN202111000494A CN113451582B CN 113451582 B CN113451582 B CN 113451582B CN 202111000494 A CN202111000494 A CN 202111000494A CN 113451582 B CN113451582 B CN 113451582B
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童汇
何海梅
喻万景
郭学益
丁治英
田庆华
季勇
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Central South University
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Abstract

The invention discloses a tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material with a chemical general formula of Li (Li)0.2M0.8(1‑x)Wx）O2‑ ySy(ii) a Wherein x is more than or equal to 0 and less than 0.1, y is more than or equal to 0 and less than 0.1, and M is at least one of Ni, Co and Mn. The invention also provides a preparation method of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material. According to the invention, tungsten disulfide is used for doping modification of the lithium-rich manganese-based positive electrode material to obtain the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material, and the initial coulombic efficiency and the cycle stability of the layered lithium-rich manganese-based positive electrode material after tungsten cations and sulfur anions are successfully doped are remarkably improved. And aiming at the precursor with the layered structure, tungsten disulfide is co-doped with tungsten and sulfur in one step in the process of preparing lithium, the preparation process is simple and easy to implement, and the two elements are doped from the same compound without introducing other impurities.

Description

Tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material and preparation method thereof
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a lithium-rich manganese-based positive electrode material and a preparation method thereof.
Background
Energy is one of the three economic branches of the 21 st century and is an important dependence on human survival. Conventional fossil fuels can provide energy, but can cause serious environmental pollution problems. There is an increasing recognition that it is important to select a high energy density, long life, reusable energy source and environmentally friendly battery energy source. Lithium ion batteries with high energy density have been the target pursued in mobile terminals, electric vehicles, and the like. In the current battery technology, graphite negative electrode materials that have been commercially available have more than 350mah-1The capacity of the positive electrode material is far lower than that of the negative electrode material, so that the factors for limiting the energy density of the lithium ion battery are mainly the positive electrode material. The key point of improving the capacity of the lithium ion battery at present is how to improve the specific capacity of the anode material on the premise of ensuring the safety.
Layered lithium-rich manganese-based positive electrode material xLi2MnO3•(1-x)LiMO2(0 < x < 1, M ═ Mn, Co, Ni) can be considered as LiMO2(M ═ Mn, Co, N) and Li2MnO3The solid solution or the composite oxide has the advantages of high theoretical specific capacity, wide working voltage window, good thermal stability and the like, thereby causing the extensive research of people and being expected to become the anode material of the next generation of lithium ion batteries. However, due to the structural characteristics and the complexity of the charge-discharge mechanism, the lithium-rich manganese-based positive electrode material has a series of problems of low coulombic efficiency in the first cycle, poor cycle stability, serious voltage attenuation and the like, and practical application of the lithium-rich material in the lithium ion battery is limited. In order to solve the problems, researchers propose modification methods such as surface coating, element doping, morphology optimization, acid treatment and the like, and improve the performance of the lithium-rich material from different angles.
Research shows that element doping can effectively inhibit structural change in the lithium intercalation/deintercalation process by substituting different elements in the material, thereby improving the material qualityElectrochemical properties of the material. For example, Chinese patent with publication number CN109904425A discloses an anion and cation co-doped lithium-rich manganese-based composite material and a preparation method thereof, and Nb is prepared5+Ions and F-Ion co-doping of Li1.18Ni0.15Co0.15Mn0.52O2The composite material improves the first coulombic efficiency of the material, but the capacity retention rate of the material is only 84.1% after the material is cycled for 100 times under the multiplying power of 0.5C, and the defect of poor long-period cycling stability cannot be solved. Moreover, the sol-gel method has certain uncontrollable property and low yield, and is not suitable for large-scale production.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the background technology and provide a tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material which is good in cycle stability, high in first coulombic efficiency and simple in doping process and a preparation method thereof. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material has a chemical general formula of Li (Li)0.2M0.8(1-x)Wx）O2-ySy(ii) a Wherein x is more than or equal to 0 and less than 0.1, y is more than or equal to 0 and less than 0.1, and M is at least one of Ni, Co and Mn. The doping amount is too large, and doping elements can hardly enter the material crystal lattice to achieve the expected effect; the content of active metal capable of providing capacity is too low, which can cause the discharge capacity of the battery to be reduced; moreover, the conductivity of the doped element is not good, and the excessive dosage of the doped element can cause the poor comprehensive performance of the battery.
As a general technical concept, the invention also provides a preparation method of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material, which comprises the following steps:
(1) preparing a transition metal carbonate precursor of the lithium-rich manganese-based positive electrode material by using a coprecipitation method;
(2) mixing and grinding the transition metal carbonate precursor obtained in the step (1) with lithium salt and tungsten disulfide powder to obtain a tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material precursor; the proportional relation of the transition metal carbonate precursor, the lithium salt and the tungsten disulfide powder is determined according to the proportional relation in the chemical general formula, and the lithium salt can be controlled to be slightly excessive;
(3) and (3) calcining the precursor of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the step (2), so as to obtain the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material.
In the above preparation method, preferably, the preparation of the transition metal carbonate precursor of the lithium-rich manganese-based positive electrode material by using a coprecipitation method includes the following steps:
(1) dissolving a transition metal salt to obtain a mixed salt solution, and dissolving a carbonate to obtain a precipitant solution; the transition metal salt is prepared according to the proportion relation in the chemical general formula;
(2) pumping the mixed salt solution obtained in the step (1) into a reaction kettle filled with ammonia water, simultaneously adjusting the ammonia water concentration of a reaction system by using the ammonia water, adjusting the pH value of the reaction system by using a precipitant solution, stirring for reaction, and after the reaction is completed, aging, filtering, washing and drying to obtain the transition metal carbonate precursor.
In the above preparation method, preferably, the transition metal salt is one or more of transition metal sulfate, nitrate or acetate (more preferably, sulfate of manganese, nickel and cobalt); the concentration of the transition metal salt in the mixed salt solution is 1-5 mol/L.
In the above production method, preferably, the carbonate salt includes one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate or ammonium bicarbonate (more preferably sodium carbonate); the concentration of carbonate in the precipitant solution is 1-10 mol/L.
In the above preparation method, preferably, the concentration of the ammonia water in the reaction system in the reaction kettle is maintained at 0.05-1 mol/L; the mass concentration of the ammonia water is 25-28%.
In the preparation method, preferably, the pH value of the reaction system in the reaction kettle is controlled to be 7.5-9, the stirring speed is 400-1000rpm, and the precipitation reaction time is 8-40 h. Sufficient reaction time is given for precipitation so as to enable particles to grow excellent morphology, and the morphology of the precursor directly influences the electrochemical performance of the material.
In the above preparation method, preferably, the lithium salt includes one or more of lithium carbonate, lithium hydroxide and lithium hydroxide monohydrate (more preferably, lithium carbonate).
In the preparation method, preferably, the calcination treatment comprises pre-calcination and high-temperature calcination, wherein the pre-calcination is performed by heating to 400-600 ℃ at a heating rate of 3-5 ℃/min and performing pre-calcination for 4-6 h; the high-temperature calcination is carried out at the temperature rise rate of 3-5 ℃/min to 800-950 ℃ for 10-20 h. More preferably, the temperature is raised to 500 ℃ at the temperature raising rate of 5 ℃/min and is kept for presintering for 5h, and then the temperature is raised to 900 ℃ at the temperature raising rate of 5 ℃/min and is calcined for 12 h.
In the prior art, in the lithium-rich cathode material, nickel ions in a transition metal layer easily occupy lithium vacancies in the lithium removal process, so that lithium is difficult to return to the original position in the insertion process, and the irreversible capacity loss and the lower first coulombic efficiency are caused; oxygen vacancies are easily formed in the oxygen layer, and cations in the metal layer easily occupy the oxygen vacancies in the charging and discharging processes, so that the structure of the material is changed, and the layered result is converted into a rock salt structure, so that the capacity of the material is quickly attenuated; according to the invention, tungsten disulfide is used as a raw material to realize co-doping of tungsten ions and sulfur ions, the tungsten ions with larger radius can partially replace the position of transition metal, the interlayer spacing is increased, the difficulty of nickel migration to a lithium layer is increased, and the removed lithium can be ensured to return to the original position, so that the first coulombic efficiency is improved; the sulfur anions can occupy oxygen vacancies, thereby stabilizing the material structure and playing a role in improving the cycle stability.
It is emphasized that tungsten disulfide and sulfur are co-doped in one step by the method, compared with the method of separately adopting a tungsten source and a sulfur source, such as tungsten trioxide and lithium sulfide, the method of doping by using tungsten disulfide has better doping effect, and finally obtained tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material Li (Li)0.2M0.8(1-x)Wx）O2-ySyThe electrochemical performance of (2) is more excellent.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, tungsten disulfide is used for doping modification of the lithium-rich manganese-based positive electrode material to obtain the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material, the particles of the positive electrode material are uniform, and the initial coulomb efficiency and the cycle stability of the lithium-rich manganese-based positive electrode material with a layered structure are remarkably improved after tungsten cations and sulfur anions are successfully doped.
2. Aiming at the precursor with the layered structure, tungsten disulfide is co-doped with tungsten and sulfur in one step in the process of preparing lithium, the preparation process is simple and easy to implement, two elements are doped from the same compound, the doping effect is better, other impurities are not introduced, and the tungsten and sulfur co-doped modified lithium-rich manganese-based anode material Li (Li) is successfully synthesized0.2M0.8(1-x)Wx）O2-ySy。
3. The process for preparing the tungsten and sulfur co-doped modified lithium-rich manganese-based cathode material has the advantages of low cost, simple and easy operation of a synthetic method, safety and effectiveness of batteries and the like, and is suitable for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an SEM image of the tungsten and sulfur co-doped modified lithium-rich manganese-based cathode material prepared in example 1.
Fig. 2 is an X-ray diffraction pattern of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material prepared in example 1.
Fig. 3 is a first charge-discharge curve diagram of a button cell assembled by the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material prepared in example 1 and the lithium-rich manganese-based positive electrode material prepared in comparative example 1 at a discharge rate of 0.1C.
Fig. 4 is a cycling curve diagram of a button cell assembled by the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material prepared in example 1 and the lithium-rich manganese-based positive electrode material prepared in comparative example 1 at a discharge rate of 1C.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material has a chemical general formula of Li [ Li ]0.2(Ni0.13Co0.13Mn0.54)0.99W0.01]O1.98S0.02。
The preparation method of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material comprises the following steps:
(1) preparation of a transition metal salt precursor:
according to the molar ratio of Ni: co: mn = 1: 1: 4 weighing nickel sulfate, cobalt sulfate and manganese sulfate, and dissolving in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution;
pumping the nickel-cobalt-manganese sulfate solution into a reaction kettle filled with ammonia water, adjusting the ammonia water concentration of a reaction system to be 0.1mol/L by using the ammonia water, adjusting the pH value of the reaction system to be 8.5 by using a precipitator solution, stirring at the speed of 800rpm, reacting for 30h, aging, filtering, washing and drying the obtained solution to obtain a nickel-cobalt-manganese ternary carbonate precursor Ni1/6Co1/6Mn4/ 6CO3。
(2) 0.0099mol of the nickel-cobalt-manganese ternary carbonate precursor obtained in the step (1), 0.007875mol of lithium carbonate (Li is excessive by 5%) and 0.0001mol of tungsten disulfide are mixed and ground to obtain a uniform tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material precursor;
(3) and (3) placing the precursor of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the step (2) in the air atmosphere of a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, maintaining the temperature for presintering for 5h, heating to 900 ℃ at the same heating rate, and calcining for 12h to obtain the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material.
Assembling the battery: weighing 0.2000g of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the embodiment, adding 0.0250g of conductive carbon black serving as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) serving as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, Celgard2300 as a diaphragm and 1mol/L LiPF (lithium ion particle Filter) in a vacuum glove box6EC: DMC: DEC (volume ratio 1: 1: 1) is used as electrolyte, and a CR2025 button cell is assembled.
As shown in fig. 1, the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material prepared in this embodiment is a secondary particle with a smooth surface and a good sphericity, and has a particle size of about 15 μm.
As shown in fig. 2, the XRD peak shape of the tungsten and sulfur co-doped modified lithium-rich manganese-based cathode material prepared in this example is complete and sharp, which indicates that the development degree of the layered structure of the material is good.
As shown in fig. 3, the first discharge capacity of the assembled battery of this example was 259.6mAh/g at 0.1C and the first coulombic efficiency was 81.61% in the voltage range of 2.0-4.8V.
As shown in fig. 4, the battery assembled in this example has a capacity retention rate of 94.94% when the battery is cycled for 100 cycles at a charge-discharge rate of 1C in a voltage range of 2.0-4.8V.
Example 2:
a tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material has a chemical general formula of Li [ Li ]0.2(Ni0.13Co0.13Mn0.54)0.98W0.02]O1.96S0.04。
The preparation method of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material comprises the following steps:
(1) preparation of a transition metal salt precursor:
according to the molar ratio of Ni: co: mn = 1: 1: 4 weighing nickel sulfate, cobalt sulfate and manganese sulfate, and dissolving in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution;
pumping the nickel-cobalt-manganese sulfate solution into a reaction kettle filled with ammonia water, adjusting the ammonia water concentration of a reaction system to be 0.1mol/L by using the ammonia water, adjusting the pH value of the reaction system to be 8.5 by using a precipitator solution, stirring at the speed of 800rpm, reacting for 30h, aging, filtering, washing and drying the obtained solution to obtain a nickel-cobalt-manganese ternary carbonate precursor Ni1/6Co1/6Mn4/ 6CO3。
(2) Mixing and grinding 0.0049mol of the nickel-cobalt-manganese ternary carbonate precursor obtained in the step (1), 0.0039375mol of lithium carbonate (Li is excessive by 5%) and 0.0001mol of tungsten disulfide to obtain a uniform tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material precursor;
(3) and (3) placing the precursor of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the step (2) in the air atmosphere of a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, maintaining the temperature for presintering for 5h, heating to 900 ℃ at the same heating rate, and calcining for 12h to obtain the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material.
Assembling the battery: weighing 0.2000g of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the embodiment, adding 0.0250g of conductive carbon black serving as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) serving as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, Celgard2300 as a diaphragm and 1mol/L LiPF (lithium ion particle Filter) in a vacuum glove box6EC: DMC: DEC (volume ratio 1: 1: 1) is used as electrolyte, and a CR2025 button cell is assembled.
The battery assembled in the embodiment has a first discharge capacity of 253.4mAh/g at 0.1C and a first coulombic efficiency of 80.32% within a voltage range of 2.0-4.8V, and has a capacity retention rate of 92.86% after 100 cycles of 1C charge-discharge multiplying power.
Example 3:
a tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material has a chemical general formula of Li [ Li ]0.2(Ni0.13Co0.13Mn0.54)0.99W0.01]O1.98S0.02。
The preparation method of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material comprises the following steps:
(1) preparation of a transition metal salt precursor:
according to the molar ratio of Ni: co: mn = 1: 1: 4 weighing nickel sulfate, cobalt sulfate and manganese sulfate, dissolving in deionized water to prepare 1mol/L mixed metal salt solution; preparing 1mol/L sodium carbonate precipitant solution;
pumping the nickel-cobalt-manganese sulfate solution into a reaction kettle filled with ammonia water, adjusting the ammonia water concentration of a reaction system to be 0.08mol/L by using the ammonia water, adjusting the pH value of the reaction system to be 8 by using a precipitator solution, stirring at the speed of 600rpm, reacting for 20 hours, aging, filtering, washing and drying the obtained solution to obtain a nickel-cobalt-manganese ternary carbonate precursor Ni1/6Co1/6Mn4/6CO3。
(2) Mixing and grinding 0.0049mol of the nickel-cobalt-manganese ternary carbonate precursor obtained in the step (1), 0.007875mol of lithium hydroxide (Li is excessive by 5%) and 0.0001mol of tungsten disulfide to obtain a uniform tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material precursor;
(3) and (3) placing the precursor of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the step (2) in the air atmosphere of a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min, maintaining the temperature for presintering for 5h, heating to 850 ℃ at the same heating rate, and calcining for 15h to obtain the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material.
Assembling the battery: 0.2000g of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the example was weighed, and 0.0250g of conductive carbon black as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride)Alkene) as adhesive, mixing uniformly, coating on aluminum foil to obtain positive plate, placing metal lithium plate as negative electrode in vacuum glove box, using Celgard2300 as diaphragm, 1mol/L LiPF6EC: DMC: DEC (volume ratio 1: 1: 1) is used as electrolyte, and a CR2025 button cell is assembled.
The battery assembled in the embodiment has a first discharge capacity of 246.2mAh/g at 0.1C and a first coulombic efficiency of 79.81% within a voltage range of 2.0-4.8V, and has a capacity retention rate of 87.65% after 100 cycles of 1C charge-discharge multiplying power.
Example 4:
a tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material has a chemical general formula of Li [ Li ]0.2(Ni0.2Mn0.6)0.99W0.01]O1.98S0.02。
The preparation method of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material comprises the following steps:
(1) preparation of a transition metal salt precursor:
according to the molar ratio of Ni: mn = 1: 3 weighing nickel sulfate, cobalt sulfate and manganese sulfate, dissolving in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution;
pumping the nickel-manganese sulfate solution into a reaction kettle filled with ammonia water, adjusting the ammonia water concentration of the reaction system to be 0.2mol/L by using the ammonia water, adjusting the pH value of the reaction system to be 8 by using a precipitator solution, stirring at the speed of 750rpm, reacting for 15h, aging, filtering, washing and drying the obtained solution to obtain a nickel-manganese binary carbonate precursor Ni0.25Mn0.75CO3。
(2) 0.0099mol of the nickel-cobalt-manganese ternary carbonate precursor obtained in the step (1), 0.007875mol of lithium carbonate (Li is excessive by 5%) and 0.0001mol of tungsten disulfide are mixed and ground to obtain a uniform tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material precursor;
(3) and (3) placing the precursor of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the step (2) in the air atmosphere of a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, maintaining the temperature for presintering for 5h, heating to 900 ℃ at the same heating rate, and calcining for 15h to obtain the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material.
Assembling the battery: weighing 0.2000g of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the embodiment, adding 0.0250g of conductive carbon black serving as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) serving as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, Celgard2300 as a diaphragm and 1mol/L LiPF (lithium ion particle Filter) in a vacuum glove box6EC: DMC: DEC (volume ratio 1: 1: 1) is used as electrolyte, and a CR2025 button cell is assembled.
The battery assembled in the embodiment has a first discharge capacity of 261.6mAh/g at 0.1C and a first coulombic efficiency of 77.85% within a voltage range of 2.0-4.8V, and has a capacity retention rate of 90.68% after 100 cycles of 1C charge-discharge multiplying power.
Comparative example 1:
the preparation method of the lithium-rich manganese-based cathode material comprises the following steps:
(1) preparation of a transition metal salt precursor:
according to the molar ratio of Ni: co: mn = 1: 1: 4 weighing nickel sulfate, cobalt sulfate and manganese sulfate, and dissolving in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution;
pumping the nickel-cobalt-manganese sulfate solution into a reaction kettle filled with ammonia water, adjusting the ammonia water concentration of a reaction system to be 0.1mol/L by using the ammonia water, adjusting the pH value of the reaction system to be 8.5 by using a precipitator solution, stirring at the speed of 800rpm, reacting for 30h, aging, filtering, washing and drying the obtained solution to obtain a nickel-cobalt-manganese ternary carbonate precursor Ni1/6Co1/6Mn4/ 6CO3。
(2) Mixing and grinding 0.01mol of the nickel-cobalt-manganese ternary carbonate precursor obtained in the step (1) and 0.007875mol of lithium carbonate (Li is excessive by 5%) to obtain a lithium-rich manganese-based positive electrode material precursor of the lithium ion battery;
(3) placing the precursor of the lithium-rich manganese-based positive electrode material obtained in the step (2) in the air atmosphere of a muffle furnace toHeating to 500 ℃ at a heating rate of 5 ℃/min, maintaining the temperature for presintering for 5h, heating to 900 ℃ at the same heating rate, and calcining for 15h to obtain the Li [ Li ] manganese-based positive electrode material0.2Ni0.13Co0.13Mn0.54]O2。
Assembling the battery: weighing 0.2000g of the lithium-rich manganese-based positive electrode material obtained in the comparative example, adding 0.0250g of conductive carbon black serving as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) serving as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, Celgard2300 as a diaphragm and 1mol/L LiPF in a vacuum glove box6EC: DMC: DEC (volume ratio 1: 1: 1) is used as electrolyte, and a CR2025 button cell is assembled.
As shown in fig. 3, the battery assembled in the present comparative example had a first discharge capacity of 235.6mAh/g and a first coulombic efficiency of 72.89% at 0.1C in a voltage range of 2.0 to 4.8V.
As shown in fig. 4, the battery assembled in this comparative example has a capacity retention rate of 75.75% when the battery is cycled for 100 cycles at a charge and discharge rate of 1C in a voltage range of 2.0-4.8V.
Comparative example 2:
the preparation method of the lithium-rich manganese-based cathode material comprises the following steps:
(1) preparation of a transition metal salt precursor:
according to the molar ratio of Ni: co: mn = 1: 1: 4 weighing nickel sulfate, cobalt sulfate and manganese sulfate, and dissolving in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution;
pumping the nickel-cobalt-manganese sulfate solution into a reaction kettle filled with ammonia water, adjusting the ammonia water concentration of a reaction system to be 0.1mol/L by using the ammonia water, adjusting the pH value of the reaction system to be 8.5 by using a precipitator solution, stirring at the speed of 800rpm, reacting for 30h, aging, filtering, washing and drying the obtained solution to obtain a nickel-cobalt-manganese ternary carbonate precursor Ni1/6Co1/6Mn4/ 6CO3。
(2) Mixing and grinding 0.005mol of the nickel-cobalt-manganese ternary carbonate precursor obtained in the step (1) and 0.007875mol of lithium hydroxide (Li is excessive by 5%) to obtain a lithium-rich manganese-based positive electrode material precursor;
(3) putting the precursor of the lithium-rich manganese-based positive electrode material obtained in the step (2) in a muffle furnace air atmosphere, heating to 450 ℃ at a heating rate of 5 ℃/min, keeping the temperature for presintering for 5h, heating to 850 ℃ at the same heating rate, and calcining for 15h to obtain the lithium-rich manganese-based positive electrode material Li [ Li ] Li0.2Ni0.13Co0.13Mn0.54]O2。
Assembling the battery: weighing 0.2000g of the lithium-rich manganese-based positive electrode material obtained in the comparative example, adding 0.0250g of conductive carbon black serving as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) serving as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, taking a metal lithium plate as a negative electrode and Celgard2300 as a diaphragm in a vacuum glove box, wherein the ratio of 1mol/L of LiPF 6/EC: DMC: DEC (volume ratio 1: 1: 1) is used as electrolyte, and a CR2025 button cell is assembled.
The battery assembled by the comparative example has the first discharge capacity of 228.6mAh/g at 0.1C and the first coulombic efficiency of 71.53% within the voltage range of 2.0-4.8V, and has the capacity retention rate of 73.68% after 100 cycles of 1C charge-discharge multiplying power.
Comparative example 3:
the preparation method of the lithium-rich manganese-based cathode material comprises the following steps:
(1) preparation of a transition metal salt precursor:
according to the molar ratio of Ni: mn = 1: 3 weighing nickel sulfate, cobalt sulfate and manganese sulfate, dissolving in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution;
pumping the nickel-manganese sulfate solution into a reaction kettle filled with ammonia water, adjusting the ammonia water concentration of the reaction system to be 0.2mol/L by using the ammonia water, adjusting the pH value of the reaction system to be 8 by using a precipitator solution, stirring at the speed of 750rpm, reacting for 15h, aging, filtering, washing and drying the obtained solution to obtain a nickel-manganese binary carbonate precursor Ni0.25Mn0.75CO3。
(2) Mixing and grinding 0.001mol of the nickel-cobalt-manganese binary carbonate precursor obtained in the step (1) and 0.007875mol of lithium carbonate (Li is excessive by 5%) to obtain a lithium-rich manganese-based positive electrode material precursor;
(3) putting the precursor of the lithium-rich manganese-based positive electrode material obtained in the step (2) in a muffle furnace air atmosphere, heating to 500 ℃ at a heating rate of 5 ℃/min, keeping the temperature for presintering for 5h, heating to 900 ℃ at the same heating rate, and calcining for 15h to obtain the lithium-rich manganese-based positive electrode material Li [ Li ] Li0.2Ni0.2Mn0.6]O2。
Assembling the battery: weighing 0.2000g of the lithium-rich manganese-based positive electrode material of the lithium ion battery obtained in the comparative example, adding 0.0250g of conductive carbon black as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, taking a metal lithium plate as a negative electrode, taking Celgard2300 as a diaphragm, and adding 1mol/L LiPF 6/EC: DMC: DEC (volume ratio 1: 1: 1) is used as electrolyte, and a CR2025 button cell is assembled.
The battery assembled by the comparative example has the first discharge capacity of 246.6mAh/g at 0.1C and the first coulombic efficiency of 70.53% within the voltage range of 2.0-4.8V, and has the capacity retention rate of 73.23% after 100 cycles of 1C charge-discharge multiplying power.
Comparative example 4:
the preparation method of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material comprises the following steps:
(1) preparation of a transition metal salt precursor:
according to the molar ratio of Ni: co: mn = 1: 1: 4 weighing nickel sulfate, cobalt sulfate and manganese sulfate, and dissolving in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution;
pumping the nickel-cobalt-manganese sulfate solution into a reaction kettle filled with ammonia water, adjusting the ammonia water concentration of a reaction system to be 0.1mol/L by using the ammonia water, adjusting the pH value of the reaction system to be 8.5 by using a precipitator solution, stirring at the speed of 800rpm, reacting for 30h, aging, filtering, washing and drying the obtained solution to obtain a nickel-cobalt-manganese ternary carbonate precursor Ni1/6Co1/6Mn4/ 6CO3。
(2) Mixing and grinding 0.0049mol of the nickel-cobalt-manganese ternary carbonate precursor obtained in the step (1), 0.0001mol of tungsten trioxide, 0.0002mol of lithium sulfide and 0.0037375mol of lithium carbonate (Li is excessive by 5%) to obtain a uniform tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material precursor;
(3) and (3) placing the precursor of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the step (2) in the air atmosphere of a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, maintaining the temperature for presintering for 5h, heating to 900 ℃ at the same heating rate, and calcining for 12h to obtain the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material.
Assembling the battery: weighing 0.2000g of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the embodiment, adding 0.0250g of conductive carbon black serving as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) serving as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, Celgard2300 as a diaphragm and 1mol/L LiPF (lithium ion particle Filter) in a vacuum glove box6EC: DMC: DEC (volume ratio 1: 1: 1) is used as electrolyte, and a CR2025 button cell is assembled.
The battery assembled by the comparative example has the first discharge capacity of 245.4mAh/g at 0.1C and the first coulombic efficiency of 75.32 percent in the voltage range of 2.0-4.8V, and has the capacity retention rate of 79.87 percent after being cycled for 100 circles under the charge-discharge rate of 1C.

Claims (1)

1. The preparation method of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material is characterized in that the lithium-rich manganese-based positive electrode material is of a layered structure and is LiMO2And Li2MnO3A solid solution or a composite oxide of the composition; the chemical general formula of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material is Li [ Li ]0.2(Ni0.13Co0.13Mn0.54)0.99W0.01]O1.98S0.02(ii) a The preparation method comprises the following steps:
(1) preparation of a transition metal salt precursor:
according to the molar ratio of Ni: co: mn = 1: 1: 4 weighing nickel sulfate, cobalt sulfate and manganese sulfate, and dissolving in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution;
pumping the nickel-cobalt-manganese sulfate solution into a reaction kettle filled with ammonia water, adjusting the ammonia water concentration of a reaction system to be 0.1mol/L by using the ammonia water, adjusting the pH value of the reaction system to be 8.5 by using a precipitator solution, stirring at the speed of 800rpm, reacting for 30h, aging, filtering, washing and drying the obtained solution to obtain a nickel-cobalt-manganese ternary carbonate precursor Ni1/6Co1/6Mn4/6CO3；
(2) 0.0099mol of the nickel-cobalt-manganese ternary carbonate precursor obtained in the step (1), 0.007875mol of lithium carbonate and 0.0001mol of tungsten disulfide are mixed and ground to obtain a uniform tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material precursor;
(3) and (3) placing the precursor of the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material obtained in the step (2) in the air atmosphere of a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, maintaining the temperature for presintering for 5h, heating to 900 ℃ at the same heating rate, and calcining for 12h to obtain the tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material.
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