CN116190629A - Cation doped lithium-rich manganese-based positive electrode material and preparation method thereof - Google Patents

Cation doped lithium-rich manganese-based positive electrode material and preparation method thereof Download PDF

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CN116190629A
CN116190629A CN202310134913.1A CN202310134913A CN116190629A CN 116190629 A CN116190629 A CN 116190629A CN 202310134913 A CN202310134913 A CN 202310134913A CN 116190629 A CN116190629 A CN 116190629A
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lithium
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吴雪艳
万靖哲
王开学
陈接胜
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Shanghai Jiaotong University
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    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
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Abstract

The invention discloses a cation doped lithium-rich manganese-based positive electrode material and a preparation method thereof, wherein the chemical general formula of the cation doped lithium-rich manganese-based positive electrode material is mLi 2 Mn 1‑x O 3 A x ·(1‑m)LiTMO 2 A is W and/or Se, and W is synthesized by hydrothermal method 6+ And/or Se 6+ The doped manganese dioxide is used as a precursor, and is subjected to high-temperature solid phase reaction with a nickel source, a cobalt source and a lithium source to obtain the nanoscale lithium-rich manganese-based positive electrode material, wherein the doping amount of cations is 0.5-10%. By combining W 6+ And/or Se 6+ The doped lithium-rich manganese-based positive electrode material remarkably improves the rate capability of the positive electrode material and is beneficial to improving the stability of crystal lattices. Hydrothermal reaction for synthesizing MnO 2 The doping element can be added in the process of (a)The doping element is doped to the target position more accurately, and the doping element can be ensured to be dispersed in the bulk phase of the material more uniformly instead of being gathered on the surface of the material, so that the lattice structure of the material is controlled more widely.

Description

Cation doped lithium-rich manganese-based positive electrode material and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a cation doped lithium-rich manganese-based positive electrode material and a preparation method thereof.
Background
Lithium ion batteries have received much attention as a new energy storage device that is environmentally friendly, and since commercialization in the last 90 th century, lithium ion batteries have been widely used in the fields of portable electronic devices, electric vehicles, and large-scale energy storage. In the last decade, research into positive electrodes of lithium ion batteries has been mainly focused on spinel structured LiCoO 2 And LiMn 2 O 4 LiFePO of olivine structure 4 And their derivatives. Although LiCoO 2 And LiFePO 4 All have successfully achieved large-scale commercial applications, but they still suffer from a number of challenges, such as LiCoO 2 After delithiation, the structure is unstable, and the lithium ion battery is easy to react with electrolyte in a certain side reaction, so that irreversible capacity loss is caused, and safety problems are caused. At the same time their lower available capacity (theoretical capacity < 200 mAh/g) has not been a way to meet the ever-increasing demand for longer duration electric vehicles. Therefore, the development of the lithium ion battery anode material with high specific capacity, high stability, high safety and low cost becomes a key for breaking through the bottleneck of energy development at present.
In various material systems, the layered material is paid attention to because of higher theoretical capacity, and the layered lithium-rich manganese-based positive electrode material has theoretical specific capacity of up to 250mAh/g and is considered as the next-generation high-performance lithium ion battery positive electrode material with great research value. The chemical formula of the lithium-rich manganese-based positive electrode material can be expressed as xLi 2 MnO 3 ·(1-x)LiMO 2 It is generally considered to be composed of Li of layered structure 2 MnO 3 And LiMO 2 Composition of Li 2 MnO 3 One third of Li in phase + By Mn 4+ Substituted, monoclinic, space group C/2m, liMO 2 Similar to the layered lithium cobaltate structure, the space group is R-3m. The special structure brings about the characteristic that anions and cations of the lithium-rich manganese-based anode material participate in electrochemical reaction at the same time, which provides additional capacity for the cathode material, and how to better stabilize lattice oxygen and promote the cycling stability of the material is the key point of the current research. Surface treatment, surface coating and anion doping are mostly adopted at present to improve the stability of materials, but the methods are often accompanied by the loss of specific capacity. Therefore, the search for a modification method for synergistically optimizing the specific capacity and the cycle stability of the lithium-rich manganese-based positive electrode material is a difficult problem to be solved.
Disclosure of Invention
Aiming at the technical problems, the invention provides a cation doped lithium-rich manganese-based positive electrode material and a preparation method thereof, and the positive electrode material is prepared by mixing W 6+ And/or Se 6+ The doped lithium-rich manganese-based positive electrode material remarkably improves the rate capability of the positive electrode material and is beneficial to improving the stability of crystal lattices.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a cation doped lithium-rich manganese-based positive electrode material has a chemical formula of mLi 2 Mn 1-x O 3 A x ·(1-m)LiTMO 2 A is W and/or Se, x is more than or equal to 0.005 and less than or equal to 0.1, the cation doped lithium-rich manganese-based positive electrode material is prepared by taking cation doped manganese dioxide synthesized by a hydrothermal method as a precursor, carrying out high-temperature solid phase reaction on the precursor and a nickel source, a cobalt source and a lithium source to obtain the nanoscale lithium-rich manganese-based positive electrode material, and the molar doping amount of the cations is 0.5-10%.
By doping tungsten ions and/or selenium ions into the lithium-rich manganese-based positive electrode material, liMO in the material can be doped 2 And Li (lithium) 2 MnO 3 The proportion of the crystal domain is regulated and controlled, so that the average valence state of manganese in the material is regulated and controlled, the Jahn-Teller effect generated in the material circulation process is inhibited, and the Mn in the material circulation process is relieved 2+ To provide a longer cycle life for the material. In additionThe strength of the W-O bond is also stronger than that of the Mn-O bond, and the introduction of tungsten element also improves the stability of lattice oxygen, so that irreversible oxygen loss can be reduced, and the first-circle coulomb efficiency and the cycle stability of the material are improved. The selenium particles improve the neighbor atomic structure around Mn ions by replacing Mn in the bulk phase, adjust bond length to improve stability, and optimize the cycle stability and rate capability of the cathode material. And when the molar ratio of cations is in the range of 0.6-2.4%, the cooperative optimization of the cycle stability and the multiplying power performance of the material can be achieved, the multiplying power performance of the material is not obviously improved under the condition of small doping amount, but when the doping amount is too large, the lattice structure of the material is distorted, so that the cycle stability of the material is rapidly reduced.
Based on the same inventive concept, the invention also provides a preparation method of the cation doped lithium-rich manganese-based positive electrode material, which comprises the following steps:
s1: dispersing a manganese source, a cation-doped salt solution, nitric acid and an oxidant in an aqueous solution, and synthesizing cation-doped manganese dioxide by a hydrothermal method;
s2: uniformly mixing the cation doped manganese dioxide obtained in the step S1 with a cobalt source, a nickel source and a lithium source through mechanical grinding, and roasting at a high temperature to obtain the cation doped lithium-rich manganese-based anode material;
wherein the doping cation is Se 6+ Or W 6+ Or Se 6+ And W is 6+ Mixing.
Preferably, the oxidant is dispersed in a dilute solution of nitric acid to obtain a mixed solution A; the hydrothermal method in the step S1 is to disperse a manganese source and salt doped with cations in an aqueous solution according to a doping proportion to obtain a mixed solution B;
mixing the mixed solution A and the mixed solution B according to the volume ratio of 1:1, performing hydrothermal reaction at the temperature of 80-250 ℃, and performing suction filtration, washing and drying after the reaction is finished;
the dilute nitric acid solution is a mixed solution of concentrated nitric acid and water in a volume ratio of 1:40-1:100, the obtained product is dispersed in deionized water, 200-500mL of deionized water is used for washing the product, and then 20-50mL of ethanol is used for washing the material so as to accelerate the drying speed, and the product is dried at the temperature of 40-120 ℃.
Preferably, the mixed solution B is added into the mixed solution A at a speed of 2-16mL/min, and stirred for 1-10h to be uniformly mixed, and the morphology of the obtained material can be regulated by adopting the mode of slowly adding the oxidant and the nitric acid into a reaction system.
Preferably, the manganese source is selected from anhydrous Mn (CH) 3 COO) 2 、Mn(CH 3 COO) 2 ·4H 2 O, anhydrous Mn (NO) 3 ) 2 、Mn(NO 3 ) 2 ·4H 2 O, anhydrous MnC 2 O 4 、MnC 2 O 4 ·2H 2 One or more of O.
Preferably, the cobalt source is selected from the group consisting of anhydrous Co (CH 3 COO) 2 、Co(CH 3 COO) 2 ·4H 2 O, anhydrous Co (NO) 3 ) 2 、Co(NO 3 ) 2 ·6H 2 O, anhydrous C DEG C 2 O 4 One or more of them.
Preferably, the nickel source is selected from the group consisting of anhydrous Ni (CH) 3 COO) 2 、Ni(CH 3 COO) 2 ·4H 2 O, anhydrous Ni (NO) 3 ) 2 、Ni(NO 3 ) 2 ·4H 2 O, anhydrous NiC 2 O 4 One or more of them.
Preferably, the doping W 6+ The salt solution is selected from Na 2 WO 4 ·2H 2 O, anhydrous Na 2 WO 4 、(NH 4 ) 2 WO 4 One or more of the following;
the doped Se 6+ The salt solution is one or more selected from selenium powder, selenate and potassium selenate.
Preferably, the oxidizing agent is potassium permanganate.
Preferably, the mechanical grinding in the step S2 is two-step mechanical grinding of the cation doped manganese dioxide obtained in the step S1 and a cobalt source, a nickel source and a lithium source through wet grinding and dry grinding, and a proper amount of ethanol is added as a grinding aid during the wet grinding.
Preferably, the high-temperature roasting in the step S2 adopts a two-step sintering method, wherein the first-step sintering is carried out for 3-20 hours at the temperature of 300-600 ℃ in an oxygen or air atmosphere, and the second-step sintering is carried out for 3-20 hours at the temperature of 600-1000 ℃ in the oxygen or air atmosphere.
By adopting the technical scheme, the invention has the following advantages and positive effects compared with the prior art:
according to the invention, by doping tungsten ions or selenium ions into the lithium-rich manganese-based positive electrode material, compared with an undoped material, the multiplying power performance of the doped material is remarkably improved, the positive ion doping expands crystal lattices of the lithium-rich manganese-based positive electrode material, the interlayer spacing is increased, the migration of lithium ions in a material body phase is facilitated, the strength of W-O bonds is higher than that of Mn-O bonds, and the stability of crystal lattices is facilitated to be improved.
Firstly, synthesizing cation doped manganese dioxide serving as a precursor by adopting a hydrothermal method, and then carrying out high-temperature solid-phase reaction on the precursor and a nickel source, a cobalt source and a lithium source to obtain a target product. Compared with the coprecipitation method adopted by most doping modification and the solid phase reaction of the compound of doping element and the precursor of lithium-rich material, the MnO is synthesized by the hydrothermal reaction 2 The method for adding the doping element in the process of (a) can more accurately incorporate the doping element into the target position, and can ensure that the doping element is more uniformly dispersed in the bulk phase of the material rather than gathered on the surface of the material, thereby playing a wider role in regulating and controlling the lattice structure of the material. In addition, the adopted raw materials are low in price, the reaction condition is mild, the method is simple to prepare, the potential of mass production is provided, and the commercialization is facilitated.
Drawings
FIG. 1 is an X-ray diffraction chart of a w-doped lithium-rich manganese-based positive electrode material prepared in example 1 of the present invention and an undoped lithium-rich manganese-based positive electrode material prepared in comparative example;
FIG. 2 is a scanning electron microscope spectrogram of the w-doped lithium-rich manganese-based cathode material prepared in example 1 of the present invention and the undoped lithium-rich manganese-based cathode material prepared in comparative example
FIG. 3 is a transmission electron microscope spectrum and a high resolution transmission electron microscope spectrum of the w-doped lithium-rich manganese-based cathode material prepared in example 1 of the present invention and the undoped lithium-rich manganese-based cathode material prepared in comparative example;
fig. 4 is a graph of electrochemical test discharge data at 2.0C rate (1c=250 mAh/g) for the w-doped lithium-rich manganese-based positive electrode material prepared in example 1 of the present invention as a positive electrode material and for the undoped lithium-rich manganese-based positive electrode material prepared in comparative example;
FIG. 5 is a graph showing the rate performance of the w-doped lithium-rich manganese-based cathode material prepared in example 1 according to the present invention as a cathode material and the undoped lithium-rich manganese-based cathode material prepared in comparative example;
fig. 6 is a graph showing the impedance of the w-doped lithium-rich manganese-based positive electrode material prepared in example 1 according to the present invention as a positive electrode material and the undoped lithium-rich manganese-based positive electrode material prepared in comparative example.
Reference numerals illustrate: in the figure, LRM is undoped lithium-rich manganese-based positive electrode material, and W-LRM is doped W 6+ Is a lithium-rich manganese-based positive electrode material.
Detailed Description
The invention provides a cation doped lithium-rich manganese-based positive electrode material and a preparation method thereof, and the positive electrode material is further described in detail below with reference to the accompanying drawings and specific examples. The advantages and features of the present invention will become more apparent from the following description.
The method comprises the steps of firstly synthesizing cation doped manganese dioxide serving as a precursor by adopting a hydrothermal method, and then carrying out high-temperature solid-phase reaction with a nickel source, a cobalt source and a lithium source to obtain a cation doped lithium-rich manganese-based positive electrode material, wherein the chemical general formula of the cation doped lithium-rich manganese-based positive electrode material is mLi 2 Mn 1-x O 3 A x ·(1-m)LiTMO 2 A is W and/or Se, x is more than or equal to 0.005 and less than or equal to 0.1, and the molar doping amount of doping elements is 0.5-10%.
Tungsten is a relatively common doping element in the catalysis field, and is mainly in natureThe tungsten exists mainly in the form of complex ions because of its small radius, high electricity price and strong polarization ability. By doping tungsten into the lithium-rich manganese-based positive electrode material, liMO in the material can be prepared 2 And Li (lithium) 2 MnO 3 The proportion of the crystal domain is regulated and controlled, so that the average valence state of manganese in the material is regulated and controlled, the Jahn-Teller effect generated in the material circulation process is inhibited, and the Mn in the material circulation process is relieved 2+ To provide a longer cycle life for the material. In addition, the strength of the W-O bond is also stronger than that of the Mn-O bond, and the introduction of tungsten element also improves the stability of lattice oxygen, so that irreversible oxygen loss can be reduced, and the first-ring coulomb efficiency and the cycle stability of the material are improved. And W is equal to 6+ The doping principle is similar to that of Se 6+ The same effect can be brought, and Mn in the material circulation process is relieved by substitution of Mn in the bulk phase, improvement of neighbor atomic structure around Mn ions, adjustment of bond length, improvement of stability, adjustment of covalent nature and the like 2+ Is dissolved in the solvent.
The specific preparation method comprises the following steps:
s1: dispersing an oxidant in a dilute solution of nitric acid to form a mixed solution A, dispersing a manganese source and salt of a doping element in an aqueous solution according to a doping proportion to form a mixed solution B, uniformly mixing the mixed solution A and the mixed solution B according to a volume ratio of 1:1, performing hydrothermal reaction at 80-250 ℃, performing suction filtration after the reaction is finished, washing a precipitate by using water and ethanol, and drying at 40-120 ℃ to obtain doped manganese dioxide;
s2: and (3) uniformly mixing the doped manganese dioxide prepared in the step (S1) with a cobalt source, a nickel source and a lithium source through mechanical grinding, and obtaining the doped lithium-rich manganese-based positive electrode material by using a high-temperature roasting method.
The dilute nitric acid solution is a mixed solution of concentrated nitric acid and water in a volume ratio of 1:40-1:100, the obtained product is dispersed in deionized water, 200-500mL of deionized water is used for washing the product, and then 20-50mL of ethanol is used for washing the material so as to accelerate the drying speed, and the product is dried at the temperature of 40-120 ℃.
Preferably, the mixed solution B is added into the mixed solution A at a speed of 2-16mL/min, and the mixed solution A is stirred for 1-10h and uniformly mixed.
Preferably, the manganese source is selected from anhydrous Mn (CH) 3 COO) 2 、Mn(CH 3 COO) 2 ·4H 2 O, anhydrous Mn (NO) 3 ) 2 、Mn(NO 3 ) 2 ·4H 2 O, anhydrous MnC 2 O 4 、MnC 2 O 4 ·2H 2 One or more of O.
Preferably, the cobalt source is selected from the group consisting of anhydrous Co (CH 3 COO) 2 、Co(CH 3 COO) 2 ·4H 2 O, anhydrous Co (NO) 3 ) 2 、Co(NO 3 ) 2 ·6H 2 O, anhydrous CoC 2 O 4 One or more of them.
Preferably, the nickel source is selected from the group consisting of anhydrous Ni (CH) 3 COO) 2 、Ni(CH 3 COO) 2 ·4H 2 O, anhydrous Ni (NO) 3 ) 2 、Ni(NO 3 ) 2 ·4H 2 O, anhydrous NiC 2 O 4 One or more of them.
Preferably, the doping W 6+ The salt solution is selected from Na 2 WO 4 ·2H 2 O, anhydrous Na 2 WO 4 、(NH 4 ) 2 WO 4 One or more of the following;
the doped Se 6+ The salt solution is one or more selected from selenium powder, selenate and potassium selenate.
Preferably, the oxidizing agent is potassium permanganate.
Preferably, the mechanical grinding in the step S2 is two-step mechanical grinding of the cation doped manganese dioxide obtained in the step S1 and a cobalt source, a nickel source and a lithium source through wet grinding and dry grinding, and a proper amount of ethanol is added as a grinding aid during the wet grinding.
Preferably, the high-temperature roasting in the step S2 adopts a two-step sintering method, wherein the first-step sintering is carried out for 3-20 hours at the temperature of 300-600 ℃ in an oxygen or air atmosphere, and the second-step sintering is carried out for 3-20 hours at the temperature of 600-1000 ℃ in the oxygen or air atmosphere.
Example 1
The preparation method of the tungsten doped lithium-rich manganese-based positive electrode material comprises the following steps:
in the first step, 1.26g of potassium permanganate was added to 40mL of an aqueous solution containing 1mL of nitric acid and stirred until the solution became purplish red, designated as solution A. 2.29g of manganese acetate tetrahydrate and 0.129g of sodium tungstate dihydrate were added to 40mL of deionized water and stirred until the solution was clear and transparent, designated solution B. Solution B was added to solution A using a peristaltic pump at 16mL/min and stirring was continued for 30min to give a brown suspension. Transferring the brown suspension into a 100mL hydrothermal reaction kettle, placing the kettle in an oven, reacting for 12 hours at 100 ℃, carrying out suction filtration, and placing the sample in the oven at 80 ℃ for drying for 12 hours to obtain the precursor W-doped manganese dioxide.
In the second step, 0.549g W doped manganese dioxide is weighed, mixed with 1.203g lithium nitrate, 0.88g nickel nitrate hexahydrate and 0.89g cobalt nitrate hexahydrate in a mortar, and a proper amount of ethanol is added as a grinding aid. After sufficient grinding, the mortar was dried in an oven at 80 ℃ for 4 hours, and then sufficiently dry-ground. And roasting the uniformly ground powder for 6 hours in an air atmosphere at 450 ℃, slightly grinding, and roasting for 10 hours in an air atmosphere at 900 ℃ to obtain the target product of the W-doped lithium-rich anode material.
Example 2
The preparation method of the tungsten doped lithium-rich manganese-based positive electrode material comprises the following steps:
in the first step, 1.26g of potassium permanganate was added to 40mL of an aqueous solution containing 1mL of nitric acid and stirred until the solution became purplish red, designated as solution A. 2.29g of manganese acetate tetrahydrate and 0.139g of ammonium tungstate were added to 40mL of deionized water and stirred until the solution was clear and transparent, designated solution B. Solution B was added to solution A at 16mL/min and stirring was continued for 30min to give a brown suspension. Transferring the brown suspension into a 100mL hydrothermal reaction kettle, placing the kettle in an oven, reacting for 12 hours at 100 ℃, carrying out suction filtration, and placing the sample in the oven at 80 ℃ for drying for 12 hours to obtain the precursor W-doped manganese dioxide.
In the second step, 0.549g W doped manganese dioxide is weighed, mixed with 1.203g lithium acetate, 0.88g nickel acetate hexahydrate and 0.89g cobalt acetate hexahydrate in a mortar, and a proper amount of ethanol is added as a grinding aid. After sufficient grinding, the mortar was dried in an oven at 80 ℃ for 4 hours, and then sufficiently dry-ground. And roasting the uniformly ground powder for 6 hours in an air atmosphere at 450 ℃, slightly grinding, and roasting for 10 hours in an air atmosphere at 900 ℃ to obtain the target product of the W-doped lithium-rich anode material.
Example 3
The preparation method of the tungsten doped lithium-rich manganese-based positive electrode material comprises the following steps:
in the first step, 1.26g of potassium permanganate was added to 40mL of an aqueous solution containing 1mL of nitric acid and stirred until the solution became purplish red, designated as solution A. 2.29g of manganese acetate tetrahydrate and 0.129g of sodium tungstate dihydrate were added to 40mL of deionized water and stirred until the solution was clear and transparent, designated solution B. Solution B was added to solution A at 16mL/min and stirring was continued for 30min to give a brown suspension. Transferring the brown suspension into a 100mL hydrothermal reaction kettle, placing the kettle in an oven, reacting for 12 hours at 100 ℃, carrying out suction filtration, and placing the sample in the oven at 80 ℃ for drying for 12 hours to obtain the precursor W-doped manganese dioxide.
In the second step, 0.549g W doped manganese dioxide is weighed, mixed with 1.203g lithium acetate, 0.88g nickel acetate hexahydrate and 0.89g cobalt acetate hexahydrate in a mortar, and a proper amount of ethanol is added as a grinding aid. After sufficient grinding, the mortar was dried in an oven at 80 ℃ for 4 hours, and then sufficiently dry-ground. And roasting the uniformly ground powder for 6 hours in an air atmosphere at 450 ℃, slightly grinding, and roasting for 10 hours in an air atmosphere at 900 ℃ to obtain the target product of the W-doped lithium-rich anode material.
Example 4
The preparation method of the selenium-doped lithium-rich manganese-based positive electrode material comprises the following steps:
in the first step, 1.26g of potassium permanganate was added to 40mL of an aqueous solution containing 1mL of nitric acid and stirred until the solution became purplish red, designated as solution A. 2.29g of manganese acetate tetrahydrate and 0.139g of potassium selenate were added to 40mL of deionized water and stirred until the solution was clear and transparent, designated solution B. Solution B was added to solution A at 16mL/min and stirring was continued for 30min to give a brown suspension. Transferring the brown suspension into a 100mL hydrothermal reaction kettle, placing the kettle in an oven, reacting for 12 hours at 100 ℃, carrying out suction filtration, and placing the sample in the oven at 80 ℃ for drying for 12 hours to obtain the precursor W-doped manganese dioxide.
Secondly, weighing 0.549g Se-doped manganese dioxide, mixing the manganese dioxide with 1.203g lithium acetate, 0.88g nickel acetate hexahydrate and 0.89g cobalt acetate hexahydrate in a mortar, and adding a proper amount of ethanol as a grinding aid. After sufficient grinding, the mortar was dried in an oven at 80 ℃ for 4 hours, and then sufficiently dry-ground. And roasting the uniformly ground powder for 6 hours in an air atmosphere at 450 ℃, slightly grinding, and roasting for 10 hours in an air atmosphere at 900 ℃ to obtain the Se-doped lithium-rich cathode material target product.
Example 5
The preparation method of the selenium-doped lithium-rich manganese-based positive electrode material comprises the following steps:
in the first step, 1.26g of potassium permanganate was added to 40mL of an aqueous solution containing 1mL of nitric acid and stirred until the solution became purplish red, designated as solution A. 2.29g of manganese acetate tetrahydrate and 0.102g of selenium powder were added to 40mL of deionized water and stirred until the solution was clear and transparent, designated solution B. Solution B was added to solution A at 16mL/min and stirring was continued for 30min to give a brown suspension. Transferring the brown suspension into a 100mL hydrothermal reaction kettle, placing the kettle in an oven, reacting for 12 hours at 100 ℃, carrying out suction filtration, and placing the sample in the oven at 80 ℃ for drying for 12 hours to obtain precursor Se-doped manganese dioxide.
In the second step, 0.559g Se-doped manganese dioxide is weighed and mixed with 1.203g lithium acetate, 0.88g nickel acetate hexahydrate and 0.89g cobalt acetate hexahydrate in a mortar, and a proper amount of ethanol is added as a grinding aid. After sufficient grinding, the mortar was dried in an oven at 80 ℃ for 4 hours, and then sufficiently dry-ground. And roasting the uniformly ground powder for 6 hours in an air atmosphere at 450 ℃, slightly grinding, and roasting for 10 hours in an air atmosphere at 900 ℃ to obtain the target product of the W-doped lithium-rich anode material.
Example 6
The preparation method of the tungsten doped lithium-rich manganese-based positive electrode material comprises the following steps:
in the first step, 1.26g of potassium permanganate was added to 40mL of an aqueous solution containing 1mL of nitric acid and stirred until the solution became purplish red, designated as solution A. 2.29g of manganese acetate tetrahydrate and 0.139g of ammonium tungstate were added to 40mL of deionized water and stirred until the solution was clear and transparent, designated solution B. Solution B was added to solution A at 16mL/min and stirring was continued for 30min to give a brown suspension. Transferring the brown suspension into a 100mL hydrothermal reaction kettle, placing the kettle in an oven, reacting for 12 hours at 100 ℃, carrying out suction filtration, and placing the sample in the oven at 80 ℃ for drying for 12 hours to obtain the precursor W-doped manganese dioxide.
In the second step, 0.549g W doped manganese dioxide is weighed, mixed with 1.213g lithium nitrate, 0.88g nickel nitrate tetrahydrate and 0.89g cobalt nitrate hexahydrate in a mortar, and proper amount of ethanol is added as grinding aid. After sufficient grinding, the mortar was dried in an oven at 80 ℃ for 4 hours, and then sufficiently dry-ground. And roasting the uniformly ground powder for 6 hours in an air atmosphere at 450 ℃, slightly grinding, and roasting for 10 hours in an air atmosphere at 900 ℃ to obtain the target product of the W-doped lithium-rich anode material.
Example 7
The preparation method of the selenium-doped lithium-rich manganese-based positive electrode material comprises the following steps:
in the first step, 1.26g of potassium permanganate was added to 40mL of an aqueous solution containing 1mL of nitric acid and stirred until the solution became purplish red, designated as solution A. 2.29g of manganese acetate tetrahydrate and 0.101g of potassium selenate were added to 40mL of deionized water and stirred until the solution was clear and transparent, designated solution B. Solution B was added to solution A at 16mL/min and stirring was continued for 30min to give a brown suspension. Transferring the brown suspension into a 100mL hydrothermal reaction kettle, placing the kettle in an oven, reacting for 12 hours at 100 ℃, carrying out suction filtration, and placing the sample in the oven at 80 ℃ for drying for 12 hours to obtain the precursor W-doped manganese dioxide.
In the second step, 0.559g Se-doped manganese dioxide is weighed and mixed with 1.213g lithium nitrate, 0.88g nickel nitrate tetrahydrate and 0.89g cobalt nitrate hexahydrate in a mortar, and a proper amount of ethanol is added as a grinding aid. After sufficient grinding, the mortar was dried in an oven at 80 ℃ for 4 hours, and then sufficiently dry-ground. And roasting the uniformly ground powder for 6 hours in an air atmosphere at 450 ℃, slightly grinding, and roasting for 10 hours in an air atmosphere at 900 ℃ to obtain the target product of the W-doped lithium-rich anode material.
Comparative example
The preparation method of the lithium-rich manganese-based positive electrode material comprises the following steps:
in the first step, 1.26g of potassium permanganate was added to 40mL of an aqueous solution containing 1mL of nitric acid and stirred until the solution became purplish red, designated as solution A. 2.29g of manganese acetate tetrahydrate was added to 40mL of deionized water and stirred until the solution was clear and transparent, designated solution B. Solution B was added to solution A at 16mL/min and stirring was continued for 30min to give a brown suspension. Transferring the brown suspension into a 100mL hydrothermal reaction kettle, placing the kettle in an oven, reacting for 12 hours at 100 ℃, carrying out suction filtration, and placing the sample in the oven at 80 ℃ for drying for 12 hours to obtain the precursor W-doped manganese dioxide.
In the second step, 0.544g of manganese dioxide is weighed, mixed with 1.213g of lithium nitrate, 0.88g of nickel nitrate tetrahydrate and 0.89g of cobalt nitrate hexahydrate in a mortar, and a proper amount of ethanol is added as a grinding aid. After sufficient grinding, the mortar was dried in an oven at 80 ℃ for 4 hours, and then sufficiently dry-ground. And roasting the uniformly ground powder for 6 hours in an air atmosphere at 450 ℃, slightly grinding, and roasting for 10 hours in an air atmosphere at 900 ℃ to obtain the target product of the lithium-rich manganese-based anode material.
Fig. 1 to 3 are an X-ray diffraction spectrum, a scanning electron microscope spectrum and a transmission electron microscope spectrum of the W-doped lithium-rich cathode material prepared in example 1 and the undoped lithium-rich manganese-based material prepared in comparative example, respectively. As can be seen from an X-ray spectrogram, the diffraction peak of the prepared W-doped lithium-rich positive electrode material accords with the characteristics of a lithium-rich layered positive electrode material, the diffraction peak of the material can well correspond to R3m and C2m point groups, the (003) peak of the material is obviously higher than the (104) peak, the Li/Ni ion mixing degree is lower, and the (018) peak and the (110) peak of the material can be obviously distinguished, so that the prepared material has a good layered structure. The high resolution electron microscopy spectra in FIG. 3 show that the W-doped is richLattice spacing d=0.439 nm of lithium material to Li 2 MnO 3 The (002) crystal face of the material accords with the crystal face of the material and is larger than the crystal face of the undoped material (d=0.434 nm), which is favorable for the transmission of lithium ions in the bulk phase of the material and improves the rate capability of the material; the scanning electron microscope spectrogram of fig. 2 and the transmission electron microscope spectrogram of fig. 3 show that the particle size of the prepared W-doped lithium-rich anode material is relatively uniform, about 300-500nm, and the nanocrystallization reduces the transmission path of lithium ions, thereby being beneficial to improving the rate performance.
The performance test is carried out on the battery after the battery is prepared from the W-doped lithium-rich layered anode material
Electrochemical performance test:
(1) Preparation of a Battery
The sample is required to be made into button-type lithium batteries before electrochemical performance testing, the sample serves as a positive electrode material of an electrode in the lithium batteries, and a lithium sheet serves as a negative electrode. The manufacturing flow comprises four processes of pretreatment, slurry preparation, electrode manufacturing and battery assembly in sequence. Mixing (mass ratio) the synthesized W-doped lithium-rich layered positive electrode material (80%) with a conductive agent Super-P (10%) and a binder polyvinylidene fluoride (10%), adding NMP, fully grinding, uniformly coating on an aluminum foil, then drying in a vacuum drying oven at 120 ℃ for 12 hours, drying, making a button cell positive electrode plate by using a cutting machine, and tabletting the positive electrode plate by using 4-6 atmospheres. And weighing the electrode slices coated with the active substances, subtracting the weight of the blank aluminum foil, calculating the weight of the active substances in each electrode slice according to the proportion of the active substances, and putting the weighed electrode slices into an argon glove box.
1M LiPF using metallic lithium sheet as negative electrode of battery 6 Ec:dmc:emc=1:1:1 electrolyte, assembly of the coin cell is carried out in an anhydrous anaerobic glove box filled with argon, assembly process of the cell:
1) Putting the positive plate in the middle of the battery shell, and dripping 1-3 drops of electrolyte by using a liquid-transferring gun;
2) Flatly paving the PP diaphragm on the electrode plate;
3) 1-3 drops of electrolyte are dripped into the center of the PP diaphragm by using a pipetting gun, and the diaphragm is completely wetted;
4) The metal lithium sheet is placed at the center of the diaphragm and cannot touch the battery shell so as to avoid short circuit of the battery;
5) Placing a stainless steel gasket and a spring piece on the lithium piece in sequence and aligning with the lithium piece;
6) And (3) covering the cathode shell, pressing with force, sealing the battery by using a sealing machine, namely, assembling, and placing the battery for 5-12h and then performing electrochemical test.
(2) Electrochemical performance test
The constant current charge-discharge cycle test of the sample is carried out on a LAND-201A battery test system, and the test voltage range is 2.0-4.8V; electrochemical impedance testing was performed on a CHIS600B electrochemical workstation (shanghai cinhua instruments).
Fig. 4 is a graph of electrochemical performance test discharge data of a W-doped lithium-rich manganese-based positive electrode material and an undoped lithium-rich manganese-based positive electrode material synthesized by the same method, and fig. 5 is a graph of rate performance of the W-doped lithium-rich manganese-based positive electrode material and an undoped lithium-rich manganese-based positive electrode material synthesized by the same method. As can be seen from the electrochemical performance test discharge data graph of fig. 4, after the lithium manganese-rich cathode material is formed into 3 circles at a 0.2C magnification, the first circle discharge specific capacity of the W-doped lithium manganese-rich cathode material is 180.2mAh/g at a 2C magnification (1c=250 mAh/g); the specific discharge capacity of the undoped lithium-rich manganese-based positive electrode material is only 131.6mAh/g, and the discharge capacity of the W-doped material after 100 circles is as high as 151.4mAh/g, and the capacity retention rate is 84%, so that the battery performance is very considerable. From the rate performance graph of fig. 6, the rate performance of the W-doped lithium-rich manganese-based positive electrode material is significantly better than that of the undoped material, and as can be seen by combining the impedance graph of fig. 6, the charge transfer impedance of the W-doped lithium-rich positive electrode material is smaller, and the lithium ion transmission rate is faster, so that the significant improvement of the rate performance of the W-doped lithium-rich positive electrode material can be well explained.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the above embodiments. Even if various changes are made to the present invention, it is within the scope of the appended claims and their equivalents to fall within the scope of the invention.

Claims (10)

1. A cation doped lithium-rich manganese-based positive electrode material is characterized in that the cation doped lithium-rich manganese-based positive electrode material is W synthesized by a hydrothermal method 6+ And/or Se 6+ The doped manganese dioxide is used as a precursor, and is subjected to high-temperature solid phase reaction with a nickel source, a cobalt source and a lithium source to obtain the nanoscale lithium-rich manganese-based positive electrode material, wherein the molar doping amount of cations is 0.5% -10%.
2. The preparation method of the cation doped lithium-rich manganese-based positive electrode material is characterized by comprising the following steps of:
s1: dispersing a manganese source, a cation-doped salt solution, nitric acid and an oxidant in an aqueous solution, and synthesizing cation-doped manganese dioxide by a hydrothermal method;
s2: uniformly mixing the cation doped manganese dioxide obtained in the step S1 with a cobalt source, a nickel source and a lithium source through mechanical grinding, and roasting at a high temperature to obtain the cation doped lithium-rich manganese-based anode material;
wherein the doping cation is Se 6+ Or W 6+ Or Se 6+ And W is 6+ Mixing.
3. The method for preparing the cation doped lithium-rich manganese-based positive electrode material according to claim 2, wherein an oxidant is dispersed in a dilute solution of nitric acid to obtain a mixed solution B; the hydrothermal method in the step S1 is to disperse a manganese source and salt doped with cations in an aqueous solution according to a doping proportion to obtain a mixed solution A;
mixing the mixed solution A and the mixed solution B according to the volume ratio of 1:1, performing hydrothermal reaction at 80-250 ℃, and performing suction filtration, washing and drying after the reaction is finished;
wherein the dilute nitric acid solution is a mixed solution of concentrated nitric acid and water in a volume ratio of 1:40-1:100.
4. The method for preparing the cation doped lithium-rich manganese-based positive electrode material according to claim 3, wherein the mixed solution B is added into the mixed solution A at a speed of 2-16mL/min, and the mixed solution A is stirred for 1-24h and uniformly mixed.
5. A method of preparing a cation doped lithium-rich manganese-based positive electrode material according to claim 2 or 3, wherein the manganese source is selected from the group consisting of anhydrous Mn (CH 3 COO) 2 、Mn(CH 3 COO) 2 ·4H 2 O, anhydrous Mn (NO) 3 ) 2 、Mn(NO 3 ) 2 ·4H 2 O, anhydrous MnC 2 O 4 、MnC 2 O 4 ·2H 2 One or more of O.
6. A method for preparing a cation doped lithium-rich manganese-based positive electrode material according to claim 2 or 3, wherein the cobalt source is selected from the group consisting of anhydrous Co (CH 3 COO) 2 、Co(CH 3 COO) 2 ·4H 2 O, anhydrous Co (NO) 3 ) 2 、Co(NO 3 ) 2 ·6H 2 O, anhydrous CoC 2 O 4 One or more of them.
7. A method for preparing a cation doped lithium-rich manganese-based positive electrode material according to claim 2 or 3, wherein the nickel source is selected from the group consisting of anhydrous Ni (CH 3 COO) 2 、Ni(CH 3 COO) 2 ·4H 2 O, anhydrous Ni (NO) 3 ) 2 、Ni(NO 3 ) 2 ·4H 2 O, anhydrous NiC 2 O 4 One or more of them.
8. A method for preparing a cation doped lithium-rich manganese-based positive electrode material according to claim 2 or 3, wherein the doped W 6+ The salt solution is selected from Na 2 WO 4 ·2H 2 O, anhydrous Na 2 WO 4 、(NH 4 ) 2 WO 4 One or more of the following;
the doped Se 6+ The salt solution is one or more selected from selenium powder, selenate and potassium selenate.
9. The method for preparing a cation-doped lithium-rich manganese-based positive electrode material according to claim 2 or 3, wherein the oxidizing agent is potassium permanganate.
10. The method for preparing the cation doped lithium-rich manganese-based positive electrode material according to claim 2, wherein the high-temperature roasting in the step S2 adopts a two-step sintering method, the first step of sintering is carried out for 3-20h at the temperature of 300-600 ℃ in an oxygen or air atmosphere, and the second step of sintering is carried out for 3-20h at the temperature of 600-1000 ℃ in an oxygen or air atmosphere.
CN202310134913.1A 2023-02-17 2023-02-17 Cation doped lithium-rich manganese-based positive electrode material and preparation method thereof Pending CN116190629A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116682972A (en) * 2023-06-16 2023-09-01 长沙理工大学 Selenium and titanium aluminum lithium phosphate double-modified lithium-rich manganese anode material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116682972A (en) * 2023-06-16 2023-09-01 长沙理工大学 Selenium and titanium aluminum lithium phosphate double-modified lithium-rich manganese anode material and preparation method thereof

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