CN113562780A - Gradient lithium-rich manganese-based positive electrode material and preparation method and application thereof - Google Patents

Gradient lithium-rich manganese-based positive electrode material and preparation method and application thereof Download PDF

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CN113562780A
CN113562780A CN202110837627.2A CN202110837627A CN113562780A CN 113562780 A CN113562780 A CN 113562780A CN 202110837627 A CN202110837627 A CN 202110837627A CN 113562780 A CN113562780 A CN 113562780A
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lithium
positive electrode
electrode material
manganese
rich manganese
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顾庆文
赛喜雅勒图
邱报
李晓
刘兆平
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention provides a gradient lithium-rich manganese-based anode material, wherein the manganese content of the gradient lithium-rich manganese-based anode material is unchanged or gradually reduced from the center of the material to the surface of the material, and the nickel and cobalt content is gradually increased. According to the method, a certain amount of nickel, cobalt and cosolvent are added during sintering to form gradient distribution of nickel-rich cobalt-rich core and manganese-rich core of the shell through diffusion at high temperature, so that the problems that a high-manganese material such as a lithium-manganese-based anode material is poor in circulation stability under high voltage, especially voltage attenuation is caused by oxygen release in a circulation process, electrolyte consumption of the material is high in the high-voltage circulation process due to the fact that the specific surface area of the material is large due to the high manganese content, particles are easy to break in the circulation process and the like are solved to a certain extent. The gradient lithium-rich manganese-based cathode material is used as the cathode material of the lithium ion battery, and the lithium-rich manganese-based cathode material with high capacity, high safety, long cycle and high compaction is suitable for preparing the lithium ion battery with high energy density and long service life.

Description

Gradient lithium-rich manganese-based positive electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a gradient lithium-rich manganese-based positive electrode material, and a preparation method and application thereof.
Background
In recent years, with the development of science and technology, the market of energy-saving and environment-friendly electric vehicles and the market of energy storage batteries are rapidly increasing, and various consumer electronic products such as smart phones, tablet computers and electronic bracelets are gradually increasing, so that the market of lithium ion batteries serving as power supplies of the products is rapidly developing. The lithium ion battery is a secondary battery with the characteristics of environmental protection, high energy density, long cycle life and the like. Along with the expansion of the use range and the increasing dependence degree of the lithium ion battery, the requirements on various performance indexes of the lithium ion battery are higher and higher, particularly the energy density and the safety performance. In terms of energy density. High energy density lithium ion batteries often require high specific energy positive and negative electrode materials, so in recent years, high nickel ternary materials are more and more emphasized by the industry, and particularly, the high capacity of materials obtained by using high voltage is gradually trend, but the high nickel ternary materials have poor thermal stability, so the safety of the high nickel ternary materials batteries is in question in recent years.
Compared with the prior art, the new rich lithium manganese-based positive electrode material as the positive electrode material simultaneously utilizes the activity of oxidation reduction of anions on the basis of oxidation reduction of transition metals so that the discharge gram capacity of the positive electrode material is more than 300mAh/g, but the rich lithium manganese-based positive electrode material has the defects of low first efficiency, voltage attenuation in the circulation process, poor rate capability and battery gas generation caused by oxygen release to influence the circulation stability performance. In addition, the low compaction density of the lithium-rich manganese-based cathode material is also one of the major bottlenecks that limit the application of the lithium-rich manganese-based cathode material.
In order to solve the problem of realizing a high-specific-energy battery system and solving the problem of poor cycling stability, attention is paid in recent years to the development of a high-specific-energy lithium ion battery positive electrode material, but the lithium-rich manganese-based positive electrode material has the remarkable characteristics of high capacity, high safety and the like, but the cycling stability is poor, particularly, the problem of high-specific-energy lithium ion battery positive electrode material is seriously needed to be solved, wherein the problem is that the voltage attenuation is brought by oxygen release in the cycling process, the electrolyte consumption of the material in the high-voltage cycling process is high due to the fact that the specific surface of the material with high manganese content is large, particles are easy to break in the cycling process, and the like.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a gradient lithium-rich manganese-based positive electrode material, and a preparation method and an application thereof, in the present invention, surface nanoparticle doping is adopted to realize gradient distribution of constituent elements of the lithium-rich manganese-based positive electrode material, so as to obtain a high-capacity lithium-rich manganese-based positive electrode material, increase surface structure stability of the lithium-rich manganese-based positive electrode material, inhibit oxygen release in a material circulation process, improve compaction density of the material, and the like.
The invention provides a gradient lithium-rich manganese-based anode material, wherein the manganese content of the gradient lithium-rich manganese-based anode material is unchanged or gradually reduced from the center of the material to the surface of the material, and the nickel and cobalt content is gradually increased.
Preferably, the gradient lithium-rich manganese-based positive electrode material is a secondary spherical particle formed by stacking primary particles.
Preferably, the primary particles are lithium-rich manganese-based anode materials with the particle size of 50-200 nm, and the particle size of secondary spherical particles of the lithium-rich manganese-based anode materials is 3-30 microns; the surface area of the lithium-rich manganese-based positive electrode material is 3-8 m2/g。
The invention also provides a preparation method of the gradient lithium-rich manganese-based positive electrode material, which comprises the following steps:
and mixing a lithium-rich manganese-based positive electrode material precursor, a lithium source compound, a nickel-containing substance, a cobalt-containing substance and a cosolvent in a solid phase, and then performing high-temperature sintering and surface modification to obtain the gradient lithium-rich manganese-based positive electrode material.
Preferably, the chemical formula of the lithium-rich manganese-based positive electrode material precursor is Li1+αMnxNiyCozO2(ii) a Wherein, 0<α<1，0.5≤x<1，0.1<y<0.5，0≤z<0.3。
Preferably, the lithium-rich manganese-based positive electrode material precursor is prepared according to the following method:
a) mixing a nickel-containing compound, a cobalt-containing compound and a manganese-containing compound with water to obtain a mixed solution, wherein the cobalt-containing compound is added or not added.
b) Mixing the mixed solution, a precipitator and a complexing agent, and carrying out coprecipitation reaction to obtain a precursor suspension containing nickel, cobalt and manganese materials;
c) and washing, filtering and drying the precursor suspension to obtain the lithium-rich manganese-based anode material precursor.
Preferably, the lithium source compound is selected from one or more of lithium carbonate, lithium hydroxide and lithium chloride;
the nickel-containing material is selected from one or more of nickel powder, nickel oxide and nickel protoxide;
the cobalt-containing substance is selected from one or more of cobalt powder, cobaltous oxide, cobalt monoxide, cobaltosic oxide and cobaltosic oxide;
the addition amount of nickel in the nickel-containing substance is 0.5-5% of the molar ratio of nickel in the precursor of the lithium-rich manganese-based positive electrode material;
the addition amount of cobalt in the cobalt-containing substance is 0.5-5% of the molar ratio of cobalt in the precursor of the lithium-rich manganese-based positive electrode material;
the cosolvent is one or more of boric acid, lithium sulfate, potassium sulfate, sodium sulfate, lithium chloride, lithium oxide, lithium carbonate, potassium chloride and sodium chloride;
the cosolvent is 0.2-2.5% of the mass of the mixture of the precursor of the lithium-rich manganese-based positive electrode material and the lithium source.
Preferably, the high-temperature sintering temperature is 750-950 ℃; the high-temperature sintering time is 8-24 h;
the surface modification is selected from surface washing or coating.
The invention also provides a high-specific energy lithium battery which comprises an anode, a cathode, a diaphragm and electrolyte, wherein the anode comprises the gradient lithium-rich manganese-based anode material.
Preferably, the negative electrode material is selected from one or more of graphite, artificial graphite, silicon carbon material, lithium metal negative electrode and lithium carbon negative electrode material;
preferably a silicon carbon material, a lithium metal negative electrode, a lithium carbon negative electrode material.
Compared with the prior art, the invention provides the gradient lithium-rich manganese-based positive electrode material, wherein the manganese content is unchanged or gradually reduced, and the nickel and cobalt content is gradually increased from the center of the material to the surface of the material. According to the method, a certain amount of nickel, cobalt and cosolvent are added during sintering to form gradient distribution of nickel-rich cobalt-rich core and manganese-rich core of the shell through diffusion at high temperature, so that the problems that a high-manganese material such as a lithium-manganese-based anode material is poor in circulation stability under high voltage, especially voltage attenuation is caused by oxygen release in a circulation process, electrolyte consumption of the material is high in the high-voltage circulation process due to the fact that the specific surface area of the material is large due to the high manganese content, particles are easy to break in the circulation process and the like are solved to a certain extent. The gradient lithium-rich manganese-based cathode material is used as the cathode material of the lithium ion battery, and the lithium-rich manganese-based cathode material with high capacity, high safety, long cycle and high compaction is suitable for preparing the lithium ion battery with high energy density and long service life.
Drawings
FIG. 1 is a schematic structural diagram of a conventional lithium-rich manganese-based positive electrode material without element gradient distribution;
FIG. 2 is a schematic structural diagram of a gradient lithium-rich manganese-based positive electrode material provided by the invention;
FIG. 3 is a process flow chart of the preparation method of the gradient lithium-rich manganese-based positive electrode material provided by the invention;
FIG. 4 is an elemental gradient profile of a starting material for a gradient lithium-rich manganese-based positive electrode material;
FIG. 5 is an SEM image of a gradient lithium-rich manganese-based cathode material provided by the present invention;
FIG. 6 is a graph of particle size distribution provided by the present invention;
FIG. 7 is a first-turn charge-discharge performance curve of the material of example 1 of the present invention;
FIG. 8 is a comparison of the cycling performance of inventive example 1 and comparative example 1.
Detailed Description
The invention provides a gradient lithium-rich manganese-based anode material, wherein the manganese content of the gradient lithium-rich manganese-based anode material is unchanged or gradually reduced from the center of the material to the surface of the material, and the nickel and cobalt content is gradually increased.
The gradient lithium-rich manganese-based positive electrode material is secondary spherical particles formed by stacking primary particles. The invention adopts the lithium-rich manganese-based positive electrode material and the constituent elements of nickel, cobalt and the like to compositely construct the positive electrode material of secondary spherical particles of the lithium-rich manganese-based positive electrode material with the gradient distribution formed from the core to the shell of nickel, cobalt and manganese, so as to obtain the lithium-rich manganese-based composite positive electrode material with high capacity, high safety, long circulation and high compaction.
The primary particles are lithium-rich manganese-based anode materials with the particle size of 50-200 nm, preferably 50, 100, 150 and 200 or any value between 50-200 nm; the particle size of the secondary spherical particles of the lithium-rich manganese-based positive electrode material is 3-30 microns, preferably 3, 10, 15, 20, 25, 30 or any value between 3-30 microns; the surface area of the lithium-rich manganese-based positive electrode material is 3-8 m2Preferably 3, 5, 8, or 3 to 8 m/g2Any value between/g.
In the invention, the manganese content of the gradient lithium-rich manganese-based positive electrode material is unchanged or gradually reduced from the center of the material to the surface of the material, and the nickel and cobalt content are gradually increased, wherein the gradual increase is linear increase, and the gradual decrease is linear decrease.
Referring to fig. 1 and fig. 2, fig. 1 is a structural schematic diagram of a conventional lithium-rich manganese-based positive electrode material without element gradient distribution, and fig. 2 is a structural schematic diagram of a gradient lithium-rich manganese-based positive electrode material provided by the present invention.
In the invention, the lithium-rich manganese-based composite positive electrode material is a composite positive electrode material with a gradient structure.
The invention also provides a preparation method of the gradient lithium-rich manganese-based positive electrode material, which comprises the following steps:
and mixing a lithium-rich manganese-based positive electrode material precursor, a lithium source compound, a nickel-containing substance, a cobalt-containing substance and a cosolvent in a solid phase, and then performing high-temperature sintering and surface modification to obtain the gradient lithium-rich manganese-based positive electrode material.
Referring to fig. 3, fig. 3 is a process flow chart of the preparation method of the gradient lithium-rich manganese-based positive electrode material provided by the invention.
Firstly, a lithium-rich manganese-based positive electrode material precursor, a lithium source compound, a nickel-containing substance, a cobalt-containing substance and a cosolvent are mixed in a solid phase manner to obtain a mixture.
Wherein the chemical formula of the precursor of the lithium-rich manganese-based positive electrode material is Li1+αMnxNiyCozO2(ii) a Wherein, 0<α<1，0.5≤x<1，0.1<y<0.5，0≤z<0.3。
In the present invention, the method for preparing the lithium-rich manganese-based positive electrode material precursor is not particularly limited, and any method known to those skilled in the art may be used.
The invention is preferably prepared as follows:
a) mixing a nickel-containing compound, a cobalt-containing compound and a manganese-containing compound with water to obtain a mixed solution, wherein the cobalt-containing compound is added or not added.
b) Mixing the mixed solution, a precipitator and a complexing agent, and carrying out coprecipitation reaction to obtain a precursor suspension containing nickel, cobalt and manganese materials;
c) and washing, filtering and drying the precursor suspension to obtain the lithium-rich manganese-based anode material precursor.
Wherein the nickel-containing compound is selected from one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate;
the cobalt-containing compound is selected from one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate;
the manganese-containing compound is selected from one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate;
and adding the mixed solution, a precipitator and a complexing agent into a coprecipitation reaction kettle through a metering pump, and performing coprecipitation reaction by controlling the temperature, the stirring speed and the reaction pH value of the reaction kettle to obtain a precursor suspension containing the nickel-cobalt-manganese material.
Wherein, the precipitant is selected from one or more of sodium carbonate and sodium hydroxide;
the complexing agent is selected from one or more of ammonia water, sodium citrate, tween and span.
The temperature is 40-70 ℃, preferably any value between 40, 50, 60, 70 or 40-70 ℃, the stirring speed is 400-700 r/min, preferably any value between 400, 500, 600, 700 or 400-700 r/min, and the pH is 7-12, preferably any value between 7, 8, 9, 10, 11, 12 or 7-12.
And after obtaining a precursor of the lithium-rich manganese-based positive electrode material, mixing the precursor of the lithium-rich manganese-based positive electrode material, a lithium source compound, a nickel-containing substance, a cobalt-containing substance and a cosolvent in a solid phase manner to obtain a mixture.
Wherein the lithium source compound is selected from one or more of lithium carbonate, lithium hydroxide and lithium chloride; the lithium source compound is added in an amount such that the lithiation ratio (i.e., the molar ratio of lithium to the transition metal) is 1.05 to 1.5, preferably 1.05, 1.1, 1.2, 1.3, 1.4, 1.5, or any value between 1.05 and 1.5.
The nickel-containing material is selected from one or more of nickel powder, nickel oxide and nickel protoxide;
the cobalt-containing substance is selected from one or more of cobalt powder, cobaltous oxide, cobalt monoxide, cobaltosic oxide and cobaltosic oxide;
the addition amount of nickel in the nickel-containing substance is 0.5-5% of the molar ratio of nickel in the lithium-rich manganese-based positive electrode material precursor, and is preferably any value between 0.5%, 1%, 2%, 3%, 4%, 5%, or 0.5-5%;
the addition amount of cobalt in the cobalt-containing substance is 0.5-5% of the molar ratio of cobalt in the lithium-rich manganese-based positive electrode material precursor, and is preferably any value between 0.5%, 1%, 2%, 3%, 4%, 5%, or 0.5-5%;
the cosolvent is one or more of boric acid, lithium sulfate, potassium sulfate, sodium sulfate, lithium chloride, lithium oxide, lithium carbonate, potassium chloride and sodium chloride;
the cosolvent is 0.2-2.5% of the mass of the mixture of the lithium-rich manganese-based positive electrode material precursor and the lithium source, and is preferably any value between 0.2%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, or 0.2-2.5%.
And then, sintering the mixture at a high temperature and carrying out surface modification to obtain the gradient lithium-rich manganese-based positive electrode material.
Wherein the temperature of the high-temperature sintering is 750-950 ℃, preferably 750, 800, 850, 900, 950, or any value between 750-950 ℃; the high-temperature sintering time is 8-24 hours, preferably 8, 10, 15, 20 and 24 or any value between 8-24 hours;
the surface modification is selected from surface washing or coating.
The surface washing is to put the material into normal-temperature water and stir the material to wash away residual alkali on the surface of the material;
the coating is surface alumina and zirconia coating, and the specific method of the coating is not particularly limited, and the coating method known to those skilled in the art can be adopted.
The invention adopts coprecipitation to synthesize the precursor of the lithium-rich manganese-based anode material, which is a precursor with a secondary spherical shape, and the elements such as nickel, cobalt and the like are introduced to diffuse under the action of the additive in the sintering process to form the lithium-rich manganese-based anode material with gradient distribution
The invention also provides a high-specific energy lithium battery which comprises an anode, a cathode, a diaphragm and electrolyte, wherein the anode comprises the gradient lithium-rich manganese-based anode material.
In the invention, the negative electrode material is selected from one or more of graphite, artificial graphite, silicon carbon material, lithium metal negative electrode and lithium carbon negative electrode material; preferably a silicon carbon material, a lithium metal negative electrode, a lithium carbon negative electrode material.
The battery can work in any voltage range after being activated by the first circle of more than 4.55V.
According to the invention, a coprecipitation method is adopted to prepare a precursor of the lithium-rich manganese-based anode material through precipitation, and the lithium-rich manganese-based anode material with the inner part forming gradient distribution for nickel, cobalt and manganese is obtained through sintering modification of elements such as lithium mixing, nickel doping and cobalt doping.
According to the method, a certain amount of nickel, cobalt and cosolvent are added during sintering to form gradient distribution of nickel-rich cobalt-rich core and manganese-rich core of the shell through diffusion at high temperature, so that the problems that a high-manganese material such as a lithium-manganese-based anode material is poor in circulation stability under high voltage, especially voltage attenuation is caused by oxygen release in a circulation process, electrolyte consumption of the material is high in the high-voltage circulation process due to the fact that specific surface area of the material with high manganese content is large, particles are easy to break in the circulation process and the like are solved to a certain extent.
The gradient lithium-rich manganese-based cathode material is used as the cathode material of the lithium ion battery, and the lithium-rich manganese-based cathode material with high capacity, high safety, long cycle and high compaction is suitable for preparing the lithium ion battery with high energy density and long service life.
For further understanding of the present invention, the following examples are provided to illustrate the gradient lithium-rich manganese-based cathode material and the preparation method and application thereof, and the scope of the present invention is not limited by the following examples.
The reagents used in the following examples are all commercially available.
Example 1:
the preparation method and the application of the gradient lithium-rich manganese-based positive electrode material comprise the following steps
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate compounds into a mixed solution of 2mol/L according to a molar ratio of 1:1: 4;
(2) adding the mixed solution, 2mol/L of precipitator sodium carbonate solution and complexing agent 1.2mol/L of ammonia water solution into a coprecipitation reaction kettle through a metering pump, controlling the temperature of the reaction kettle to be 55 ℃, stirring speed to be 500r/min, reaction pH value to be 7.5-8.5, carrying out coprecipitation reaction for 45 hours to obtain nickel-cobalt-manganese carbonate precursor suspension,
(3) washing, filtering and drying the composite material precursor suspension to obtain a lithium-rich manganese-based positive electrode material precursor containing nickel, cobalt and manganese,
(4) the precursor Ni of the lithium-rich manganese-based cathode material containing nickel, cobalt and manganese0.167Co0.167Mn0.666CO3Adding NiO containing 0.67 mol percent of nickel and Co containing 0.67 mol percent of cobalt into lithium carbonate according to the proportion that Me is 1.23O4And 2% NaCl (as cosolvent) solid phase, and sintering at high temperature to obtain Li1.2Ni0.2Co0.2Mn0.56O2Raw materials of the gradient lithium-rich manganese-based positive electrode material;
referring to fig. 4, fig. 4 is an element gradient distribution diagram of a raw material of the gradient lithium-rich manganese-based positive electrode material. As can be seen from FIG. 4, the element distribution of the SEM-EDS material shows that the contents of Ni and Co elements are gradually reduced from outside to inside without changing the content of Mn, and the overall structure of the material shows the gradient distribution of Ni and Co from the outer layer to the inner layer.
(5) Washing the raw material of the gradient lithium-rich manganese-based anode material in a reaction kettle at normal temperature, adding a solution containing 5 mass percent of aluminum for reaction, centrifuging the reaction product at 550 ℃, and sintering the reaction product to obtain Li with the surface coated with aluminum1.18Ni0.2Co0.2Mn0.56O2Gradient lithium-rich manganese-based cathode material.
Referring to fig. 5 and 6, fig. 5 is an SEM image of the gradient lithium-rich manganese-based cathode material provided by the present invention. FIG. 6 is a graph showing the particle size distribution according to the present invention.
(6) Adding 3.5% of conductive agent SP + carbon nano tube, binder PVDF and solvent NMP into the gradient lithium-rich manganese-based anode material according to the mass ratio of 5% of the anode material, adding into a batching kettle, and stirring to obtain lithium ion battery composite anode material slurry;
(7) coating the gradient lithium-rich manganese-based positive electrode material slurry on a positive electrode current collector, drying a pole piece, slicing and rolling to obtain a positive electrode material pole piece for later use,
(8) similarly, adding the negative active material silicon-carbon composite negative material with the discharge gram capacity of 850mAh/g, a conductive agent SP + carbon nano tube, a binder CMC and a solvent SBR into a batching kettle, and stirring to obtain the slurry of the negative material of the lithium ion battery;
(9) coating the negative electrode material slurry on a positive electrode current collector, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
(10) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
(11) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
(12) And (3) charging the first circle of the battery to be more than 4.55V, activating, and then circulating according to the voltage range of 2-4.45V.
Referring to fig. 7 and 8, fig. 7 is a first-turn charge and discharge performance curve of the material of inventive example 1, and fig. 8 is a cycle performance comparison of inventive example 1 and comparative example 1.
Through detection, the tap density of the material reaches 2.5g/cc, and the first-circle discharge gram capacity of the material reaches 305mAh/g within the voltage range of 2-4.8V of a half cell. The compacted density of the positive pole piece manufactured in the step 7 is up to 3.0g/cc, the first efficiency of the assembled full battery is up to 93%, the energy density of the full battery is up to 375Wh/Kg, the capacity retention rate of the full battery is 92% after 800 cycles in a voltage range of 2.8-4.45V, no gas is generated in the cycle process, and the positive pole piece is suitable for basic requirements of high-specific-energy power battery application.
Example 2
A preparation method and application of a gradient lithium-rich manganese-based positive electrode material comprise the following steps:
(1) preparing nickel sulfate, cobalt sulfate and manganese sulfate compounds into a mixed solution of 2mol/L according to a molar ratio of 1:1: 6;
(2) adding the mixed solution, 2mol/L of precipitator sodium carbonate solution and complexing agent 1.5mol/L of ammonia water solution into a coprecipitation reaction kettle through a metering pump, controlling the temperature of the reaction kettle to be 57 ℃, stirring speed to be 500r/min, reaction pH value to be 7.7-8.6, carrying out coprecipitation reaction for 55h to obtain nickel-cobalt-manganese carbonate precursor suspension,
(3) washing, filtering and drying the composite material precursor suspension to obtain a lithium-rich manganese-based positive electrode material precursor containing nickel, cobalt and manganese,
(4) the precursor Ni of the lithium-rich manganese-based cathode material containing nickel, cobalt and manganese0.125Co0.125Mn0.75CO3Adding nickel powder containing 1.2 mol% of nickel, cobalt powder containing 1.2 mol% of cobalt and 1.5 mol% of Li into lithium carbonate according to the proportion that Me is 1.12SO4(as lithium source and cosolvent) solid phase mixing and high temperature sintering to obtain Li1.25Ni0.17Co0.17Mn0.68O2Raw materials of the gradient lithium-rich manganese-based positive electrode material;
(5) washing the raw material of the gradient lithium-rich manganese-based anode material in a reaction kettle at normal temperature, and adding a solution containing 5 mass percent of zirconiumReacting, centrifuging at 450 ℃, sintering to obtain surface modification treatment Li with zirconium coated surface1.22Ni0.17Co0.17Mn0.68O2Gradient lithium-rich manganese-based positive electrode material
(6) Adding 3.5% of conductive agent SP + carbon nano tube, binder PVDF and solvent NMP into the gradient lithium-rich manganese-based anode material according to the mass ratio of 5% of the anode material, adding into a batching kettle, and stirring to obtain lithium ion battery composite anode material slurry;
(7) coating the gradient lithium-rich manganese-based positive electrode material slurry on a positive electrode current collector, drying a pole piece, slicing and rolling to obtain a positive electrode material pole piece for later use,
(8) similarly, adding the negative active material silicon-carbon composite negative material with the discharge gram capacity of 850mAh/g, a conductive agent SP + carbon nano tube, a binder CMC and a solvent SBR into a batching kettle, and stirring to obtain the slurry of the negative material of the lithium ion battery;
(9) coating the negative electrode material slurry on a positive electrode current collector, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
(10) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
(11) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
(12) Charging the first circle of the battery to more than 4.55V, activating, and circulating according to the voltage range of 2-4.45V
Through detection, the tap density of the material reaches 2.2g/cc, and the first-circle discharge gram capacity of the material reaches 315mAh/g within the voltage range of 2-4.8V of a half cell. The compacted density of the positive pole piece manufactured in the step 7 is up to 3.0g/cc, the first efficiency of the assembled full battery is up to 94%, the energy density of the full battery is up to 405Wh/Kg, the capacity retention rate of the full battery is 90% after 800 cycles in a voltage range of 2.8-4.45V, no gas is generated in the cycle process, and the positive pole piece is suitable for basic requirements of high-specific-energy power battery application.
Example 3
The preparation method and the application of the gradient lithium-rich manganese-based positive electrode material comprise the following steps
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate compounds into a mixed solution of 2mol/L according to a molar ratio of 1:1: 8;
(2) adding the mixed solution, 2mol/L of precipitator sodium carbonate solution and complexing agent 1.5mol/L of ammonia water solution into a coprecipitation reaction kettle through a metering pump, controlling the temperature of the reaction kettle to be 56 ℃, the stirring speed to be 500r/min, the reaction pH value to be 7.7-8.6, carrying out coprecipitation reaction for 55h to obtain nickel-cobalt-manganese carbonate precursor suspension,
(3) washing, filtering and drying the composite material precursor suspension to obtain a lithium-rich manganese-based positive electrode material precursor containing nickel, cobalt and manganese,
(4) the precursor Ni of the lithium-rich manganese-based cathode material containing nickel, cobalt and manganese0.1Co0.1Mn0.8CO3Adding nickel protoxide containing 2.5 mol% of nickel, cobalt oxide (II) containing 2.5 mol% of cobalt and 1.5 mol% of Na into lithium carbonate according to the proportion of Li: Me being 1.12SO4Solid phase mixing and high temperature sintering to obtain Li1.25Ni0.17Co0.17Mn0.68O2Raw materials of the gradient lithium-rich manganese-based positive electrode material;
(5) washing the raw material of the gradient lithium-rich manganese-based anode material in a reaction kettle at normal temperature, adding a solution containing 1% of zirconium for reaction, centrifuging the reaction product at 450 ℃, and sintering the reaction product to obtain Li with the surface coated with zirconium1.2Ni0.17Co0.17Mn0.68O2Gradient lithium-rich manganese-based positive electrode material
(6) Adding 3.5% of conductive agent SP + carbon nano tube, binder PVDF and solvent NMP into the gradient lithium-rich manganese-based anode material according to the mass ratio of 5% of the anode material, adding into a batching kettle, and stirring to obtain lithium ion battery composite anode material slurry;
(7) coating the gradient lithium-rich manganese-based positive electrode material slurry on a positive electrode current collector, drying a pole piece, slicing and rolling to obtain a positive electrode material pole piece for later use,
(8) similarly, adding the negative active material silicon-carbon composite negative material with the discharge gram capacity of 850mAh/g, a conductive agent SP + carbon nano tube, a binder CMC and a solvent SBR into a batching kettle, and stirring to obtain the slurry of the negative material of the lithium ion battery;
(9) coating the negative electrode material slurry on a positive electrode current collector, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
(10) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
(11) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
(12) Charging the first circle of the battery to more than 4.55V, activating, and circulating according to the voltage range of 2-4.45V
Through detection, the tap density of the material reaches 2.2g/cc, and the first-circle discharge gram capacity of the material reaches 303mAh/g within the voltage range of 2-4.8V of a half cell. The compacted density of the positive pole piece manufactured in the step 7 is up to 2.95g/cc, the first efficiency of the assembled full battery is up to 94%, the energy density of the full battery is up to 395Wh/Kg, the capacity retention rate of the full battery is 90% after 800 cycles within the voltage range of 2.8-4.45V, no gas is generated in the cycle process, and the positive pole piece is suitable for basic requirements of high-specific-energy power battery application.
Example 4
The preparation method and the application of the gradient lithium-rich manganese-based positive electrode material comprise the following steps
(1) Preparing nickel sulfate and a manganese sulfate compound into a mixed solution of 2mol/L according to the proportion of 1: 3;
(2) adding the mixed solution, 2mol/L of precipitator sodium carbonate solution and complexing agent 2.5mol/L of ammonia water solution into a coprecipitation reaction kettle through a metering pump, controlling the temperature of the reaction kettle to 65 ℃, the stirring speed to be 500r/min and the reaction pH value to be 7.7-8.6, carrying out coprecipitation reaction for 55 hours to obtain nickel-manganese carbonate precursor suspension,
(3) washing, filtering and drying the composite material precursor suspension to obtain a lithium-rich manganese-based positive electrode material precursor containing nickel, cobalt and manganese,
(4) ni is the precursor of the nickel-manganese-containing lithium-rich manganese-based positive electrode material0.25Mn0.75CO3Adding 2.5mol percent nickel-containing oxide into lithium carbonate according to the proportion that Me is 1.3Nickel (II) oxide containing cobalt in a molar ratio of 5% and 1.5% Na2SO4Solid phase mixing and high temperature sintering to obtain Li1.25Ni0.2Co0.1Mn0.65O2Raw materials of the gradient lithium-rich manganese-based positive electrode material;
(5) washing the raw material of the gradient lithium-rich manganese-based anode material in a reaction kettle at normal temperature, adding a solution containing 5 mass percent of aluminum for reaction, centrifuging the reaction product at 450 ℃, and sintering the reaction product to obtain Li with the surface coated with aluminum1.2Ni0.2Co0.1Mn0.65O2Gradient lithium-rich manganese-based positive electrode material
(6) Adding 3.5% of conductive agent SP + carbon nano tube, binder PVDF and solvent NMP into the gradient lithium-rich manganese-based anode material according to the mass ratio of 5% of the anode material, adding into a batching kettle, and stirring to obtain lithium ion battery composite anode material slurry;
(7) coating the gradient lithium-rich manganese-based positive electrode material slurry on a positive electrode current collector, drying a pole piece, slicing and rolling to obtain a positive electrode material pole piece for later use,
(8) similarly, adding the negative active material silicon-carbon composite negative material with the discharge gram capacity of 850mAh/g, a conductive agent SP + carbon nano tube, a binder CMC and a solvent SBR into a batching kettle, and stirring to obtain the slurry of the negative material of the lithium ion battery;
(9) coating the negative electrode material slurry on a positive electrode current collector, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
(10) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
(11) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
(12) Charging the first circle of the battery to more than 4.55V, activating, and circulating according to the voltage range of 2-4.45V
Through detection, the tap density of the material reaches 2.2g/cc, and the first-circle discharge gram capacity of the material reaches 295mAh/g within the voltage range of 2-4.8V of a half cell. The compacted density of the positive pole piece manufactured in the step 7 is up to 2.95g/cc, the first efficiency of the assembled full battery is up to 94%, the energy density of the full battery is up to 355Wh/Kg, the capacity retention rate of the full battery is 95% after 800 cycles within the voltage range of 2.8-4.45V, no gas is generated in the cycle process, and the positive pole piece is suitable for basic requirements of high-specific-energy power battery application.
Comparative example 1
The preparation method and the application of the lithium-rich manganese-based positive electrode material are characterized by comprising the following steps
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate compounds into a mixed solution of 2mol/L according to a molar ratio of 1:1: 4;
(2) adding the mixed solution, 2mol/L of precipitator sodium carbonate solution and complexing agent 1.2mol/L of ammonia water solution into a coprecipitation reaction kettle through a metering pump, controlling the temperature of the reaction kettle to be 55 ℃, stirring speed to be 500r/min, reaction pH value to be 7.5-8.5, carrying out coprecipitation reaction for 45 hours to obtain nickel-cobalt-manganese carbonate precursor suspension,
(3) washing, filtering and drying the composite material precursor suspension to obtain a lithium-rich manganese-based positive electrode material precursor containing nickel, cobalt and manganese,
(4) the precursor Ni of the lithium-rich manganese-based cathode material containing nickel, cobalt and manganese0.167Co0.167Mn0.666CO3Mixing with lithium carbonate in Li-Me ratio of 1.2, solid phase sintering to obtain Li1.2Ni0.2Co0.2Mn0.56O2A raw material of the lithium-rich manganese-based positive electrode material;
(5) washing the raw material of the lithium-rich manganese-based anode material in a reaction kettle at normal temperature, adding a solution containing 5 mass percent of zirconium, reacting, centrifuging, and sintering at 550 ℃ to obtain Li with the surface coated with zirconium1.18Ni0.16Co0.16Mn0.54O2Gradient lithium-rich manganese-based positive electrode material
(6) Adding 3.5% of conductive agent SP + carbon nano tube, binder PVDF and solvent NMP into the lithium-rich manganese-based anode material according to the mass ratio of 5% of the anode material, adding into a batching kettle, and stirring to obtain lithium ion battery composite anode material slurry;
(7) coating the lithium-rich manganese-based positive electrode material slurry on a positive electrode current collector, drying, slicing and rolling to obtain a positive electrode material pole piece for later use,
(8) similarly, adding the negative active material silicon-carbon composite negative material with the discharge gram capacity of 850mAh/g, a conductive agent SP + carbon nano tube, a binder CMC and a solvent SBR into a batching kettle, and stirring to obtain the slurry of the negative material of the lithium ion battery;
(9) coating the negative electrode material slurry on a positive electrode current collector, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
(10) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
(11) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
(12) And (3) charging the first circle of the battery to be more than 4.55V, activating, and then circulating according to the voltage range of 2-4.45V.
Through detection, the tap density of the material reaches 2.5g/cc, and the first-circle discharge gram capacity of the material reaches 295mAh/g within the voltage range of 2-4.8V of a half cell. The compacted density of the positive pole piece manufactured in the step 7 is 2.70g/cc, the first efficiency of the assembled full battery reaches 92%, the energy density of the full battery reaches 325Wh/Kg, the capacity retention rate of 800 cycles of the full battery within the voltage range of 2.8-4.45V is 80%, and no gas is generated in the cycle process.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The gradient lithium-rich manganese-based cathode material is characterized in that the manganese content is unchanged or gradually reduced and the nickel and cobalt content is gradually increased from the center of the material to the surface of the material.
2. The positive electrode material according to claim 1, wherein the gradient lithium-rich manganese-based positive electrode material is a secondary spherical particle in which primary particles are stacked.
3. The positive electrode material according to claim 1, wherein the primary particles are a lithium-rich manganese-based positive electrode material having a particle size of 50 to 200nm, and the secondary spherical particles of the lithium-rich manganese-based positive electrode material have a particle size of 3 to 30 μm; the surface area of the lithium-rich manganese-based positive electrode material is 3-8 m2/g。
4. The preparation method of the gradient lithium-rich manganese-based positive electrode material is characterized by comprising the following steps of:
and mixing a lithium-rich manganese-based positive electrode material precursor, a lithium source compound, a nickel-containing substance, a cobalt-containing substance and a cosolvent in a solid phase, and then performing high-temperature sintering and surface modification to obtain the gradient lithium-rich manganese-based positive electrode material.
5. The production method according to claim 4, wherein the chemical formula of the lithium-rich manganese-based positive electrode material precursor is Li1+αMnxNiyCozO2(ii) a Wherein, 0<α<1，0.5≤x<1，0.1<y<0.5，0≤z<0.3。
6. The production method according to claim 4, wherein the lithium-rich manganese-based positive electrode material precursor is produced by:
a) mixing a nickel-containing compound, a cobalt-containing compound and a manganese-containing compound with water to obtain a mixed solution, wherein the cobalt-containing compound is added or not added;
b) mixing the mixed solution, a precipitator and a complexing agent, and carrying out coprecipitation reaction to obtain a precursor suspension containing nickel, cobalt and manganese materials;
c) and washing, filtering and drying the precursor suspension to obtain the lithium-rich manganese-based anode material precursor.
7. The method according to claim 4, wherein the lithium source compound is selected from one or more of lithium carbonate, lithium hydroxide, and lithium chloride;
the nickel-containing material is selected from one or more of nickel powder, nickel oxide and nickel protoxide;
the cobalt-containing substance is selected from one or more of cobalt powder, cobaltous oxide, cobalt monoxide, cobaltosic oxide and cobaltosic oxide;
the addition amount of nickel in the nickel-containing substance is 0.5-5% of the molar ratio of nickel in the precursor of the lithium-rich manganese-based positive electrode material;
the addition amount of cobalt in the cobalt-containing substance is 0.5-5% of the molar ratio of cobalt in the precursor of the lithium-rich manganese-based positive electrode material;
the cosolvent is one or more of boric acid, lithium sulfate, potassium sulfate, sodium sulfate, lithium chloride, lithium oxide, lithium carbonate, potassium chloride and sodium chloride;
the cosolvent is 0.2-2.5% of the mass of the mixture of the precursor of the lithium-rich manganese-based positive electrode material and the lithium source.
8. The preparation method according to claim 4, wherein the temperature of the high-temperature sintering is 750-950 ℃; the high-temperature sintering time is 8-24 h;
the surface modification is selected from surface washing or coating.
9. A high specific energy lithium battery, comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the positive electrode comprises the gradient lithium-rich manganese-based positive electrode material as claimed in any one of claims 1 to 3.
10. The high specific energy lithium battery of claim 9, wherein the negative electrode material is selected from one or more of graphite, artificial graphite, silicon carbon material, lithium metal negative electrode, lithium carbon negative electrode material;
preferably a silicon carbon material, a lithium metal negative electrode, a lithium carbon negative electrode material.
CN202110837627.2A 2021-07-23 2021-07-23 Gradient lithium-rich manganese-based positive electrode material and preparation method and application thereof Pending CN113562780A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114583120A (en) * 2021-12-27 2022-06-03 武汉理工大学 Method for designing and constructing gradient structure with metal ion component on surface of lithium-rich material
CN114975983A (en) * 2022-05-06 2022-08-30 四川新锂想能源科技有限责任公司 High-nickel low-cobalt material, preparation method thereof and battery anode
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