CN111342039A - Yttrium ion modified lithium ion battery ternary positive electrode material and preparation method thereof - Google Patents

Yttrium ion modified lithium ion battery ternary positive electrode material and preparation method thereof Download PDF

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CN111342039A
CN111342039A CN202010184885.0A CN202010184885A CN111342039A CN 111342039 A CN111342039 A CN 111342039A CN 202010184885 A CN202010184885 A CN 202010184885A CN 111342039 A CN111342039 A CN 111342039A
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yttrium
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preserving heat
ion battery
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章冬云
陈秋义
王乃占
孙光翰
李卫东
杜利春
王蒙蒙
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Shanghai Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a yttrium ion modified lithium ion battery ternary cathode material and a preparation method thereof. The chemical formula of the ternary cathode material of the lithium ion battery is Li (Ni)0.6Co0.2Mn0.2)1‑ xYxO2Wherein x is more than or equal to 0.005 and less than or equal to 0.015. The preparation method comprises the following steps: adding nickel oxide, cobalt oxide, manganese dioxide, lithium carbonate and yttrium oxide into deionized water, uniformly stirring, then performing ball milling, and performing spray drying on the obtained slurry to obtain precursor powder of the ternary positive electrode material of the lithium ion battery; briquetting and calcining the obtained powder. The yttrium ion modified lithium ion battery ternary anode material obtained by the invention enlarges the interlayer spacing after replacement because the radius of yttrium ions is far larger than the ionic radius of the transition metal layer,the diffusion speed of lithium ions is accelerated, the mixed lithium-nickel discharge is reduced, and the electrochemical performance of the material is improved.

Description

Yttrium ion modified lithium ion battery ternary positive electrode material and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion battery manufacturing, and particularly relates to a yttrium ion modified lithium ion battery ternary cathode material and a preparation method thereof.
Background
The clean and efficient lithium ion secondary battery can improve sustainable and efficient energy for social development, reduce excessive dependence on traditional energy such as petroleum and the like, and reduce the pressure of ecological environment. The lithium ion battery has the outstanding advantages of long cycle life, light weight, small volume, wide voltage range, large specific capacity, no memory effect, rapid charge and discharge and the like. Through decades of technical development, a batch of lithium ion batteries with wide market application range and low price have been developed. With the change from fuel automobiles to electric automobiles which is greatly recommended in China, lithium ion batteries are coming to the opportunity of rapid development again. The development of power battery materials with high energy density, long cycle life and good safety performance is of great significance, and the positive electrode material serving as an important component of the lithium ion battery can be developed rapidly.
The nickel-cobalt-manganese ternary positive electrode material integrates the advantages of lithium cobaltate, lithium manganate and lithium nickelate, makes up the respective defects of the three materials, and shows higher discharge specific capacity, lower cost advantage and better stability. At present, the ternary material has formed a relatively stable commercial product after decades of development, and is widely applied to 3C products, portable mobile equipment, electric tools and the like. With the rapid development of electric vehicles in recent years, the share of ternary materials on power batteries is continuously improved due to the advantages of higher energy density, quick charge and discharge, good cycle performance and the like.
Along with the increase of the nickel content, the manganese element which plays a role in structural stability in the material and the cobalt element which can improve the electronic conductivity are all reduced, so that the lithium-nickel mixed-discharge phenomenon of the material is more serious, and the rate capability and the cycling stability are poor. Meanwhile, the high nickel material has high requirement on the humidity of air, and is easy to react with water and carbon dioxide to cause the battery to expand. Therefore, the stability of the lattice structure of the material can be improved by adopting an ion doping/substitution mode, the mixed arrangement of lithium and nickel is reduced, and the electrochemical performance of the material is improved by improving the conductivity.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to improve the cycling stability of the ternary cathode material of the lithium ion battery.
In order to solve the technical problem, the invention provides an yttrium ion modified lithium ion battery ternary cathode material which is characterized in that the chemical formula of the yttrium ion modified lithium ion battery ternary cathode material is Li (Ni)0.6Co0.2Mn0.2)1-xYxO2Wherein x is more than or equal to 0.005 and less than or equal to 0.015.
Preferably, the value of x is 0.005, 0.01 or 0.015.
The invention also provides a preparation method of the yttrium ion modified lithium ion battery ternary cathode material, which is characterized by comprising the following steps of:
step 1: weighing 130-136 parts of nickel oxide, 40-46 parts of cobalt oxide, 50-53 parts of manganese dioxide, 117 parts of lithium carbonate and 5-17 parts of yttrium oxide, adding into 1200 parts of deionized water by weight of 900-1200 parts, and uniformly stirring to obtain a uniform mixed solution;
step 2: adding the mixed solution obtained in the step (1) into a nano sand mill, performing ball milling for 30-80min, taking out the slurry, and performing spray drying at the temperature of 160-180 ℃ to obtain precursor powder of the ternary cathode material of the lithium ion battery;
and step 3: and (3) briquetting the powder obtained in the step (2), calcining in an oxygen atmosphere, heating to 400-550 ℃, preserving heat for 5h, heating to 750-950 ℃, preserving heat for 8-12h, and obtaining the yttrium ion modified lithium ion battery ternary cathode material after calcining.
Preferably, when x is 0.005, weighing the following raw materials in part by weight in step 1: 135 parts of nickel oxide, 45 parts of cobalt oxide, 52 parts of manganese dioxide, 117 parts of lithium carbonate and 6 parts of yttrium oxide.
More preferably, the calcination process in step 3 is: firstly, heating to 400-550 ℃ and preserving heat for 5h, then heating to 950 ℃ and preserving heat for 8h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 850 ℃ and preserving heat for 10h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 750 ℃ and preserving heat for 12h, and ending the calcination.
Preferably, when x is 0.01, weighing the following raw materials in part by weight in step 1: 134 parts of nickel oxide, 43 parts of cobalt oxide, 51.5 parts of manganese dioxide, 117 parts of lithium carbonate and 11 parts of yttrium oxide.
More preferably, the calcination process in step 3 is: firstly, heating to 400-550 ℃ and preserving heat for 5h, then heating to 950 ℃ and preserving heat for 8h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 850 ℃ and preserving heat for 10h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 750 ℃ and preserving heat for 12h, and ending the calcination.
Preferably, when x is 0.015, weighing the following raw materials in part by weight in step 1: 133 parts of nickel oxide, 41 parts of cobalt oxide, 51 parts of manganese dioxide, 117 parts of lithium carbonate and 16 parts of yttrium oxide.
More preferably, the calcination process in step 3 is: firstly, heating to 400-550 ℃ and preserving heat for 5h, then heating to 950 ℃ and preserving heat for 8h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 850 ℃ and preserving heat for 10h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 750 ℃ and preserving heat for 12h, and ending the calcination.
Firstly, adding nickel oxide, cobalt oxide, manganese dioxide, lithium carbonate and yttrium oxide into a proper amount of deionized water, uniformly mixing, pouring into a nano sand mill, grinding for 30-80min to obtain suspended matter slurry, then carrying out spray drying, briquetting, and calcining at 750-950 ℃ for 8-12h in an oxygen atmosphere to obtain the yttrium ion modified ternary cathode material of the lithium ion battery.
According to the yttrium ion modified lithium ion battery ternary cathode material, the radius of yttrium ions is far larger than that of ions of a transition metal layer, so that the interlayer spacing is enlarged after replacement, the diffusion speed of lithium ions is increased, the mixed arrangement of lithium and nickel is reduced, and the electrochemical performance of the material is improved.
The invention adopts a nano ball milling assisted high-temperature solid phase method, the particle size is controlled between 160-300nm after ball milling, precursor powder is obtained by spray drying, and then the required yttrium ion modified lithium ion battery ternary anode material is obtained by high-temperature calcination. Compared with the common coprecipitation method in the current industry, the method does not generate wastewater, has more environment-friendly production process and is beneficial to commercial popularization.
According to the yttrium ion modified lithium ion battery ternary cathode material, due to the substitution of yttrium ions, the structure stability of the material is improved, the lithium-nickel mixed discharge is reduced, the initial discharge specific capacity of the material under the multiplying power of 1C is 159.2mAh/g, the capacity retention rate is 92.2% after 100 cycles of continuous circulation, and the cycle performance of the material is obviously improved.
Drawings
FIG. 1 is an XRD spectrum of the yttrium ion modified lithium ion battery ternary cathode material obtained in example 1;
FIG. 2 is an SEM image of the yttrium ion modified ternary cathode material of the lithium ion battery obtained in example 1;
FIG. 3 is an XRD crystallographic modification pattern of the yttrium ion modified lithium ion battery ternary cathode material obtained in example 1;
fig. 4 is a cycle performance map of the yttrium ion modified lithium ion battery ternary cathode material obtained in example 1.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
An yttrium ion modified lithium ion battery ternary positive electrode material comprises the following raw materials in parts by weight:
nickel oxide: 135 parts of (A);
cobalt oxide: 35 parts of (B);
manganese dioxide: 52 parts of (1);
lithium carbonate: 117 parts of (a);
yttrium oxide: 6 parts.
The preparation process specifically comprises the following steps:
1) 135 parts by weight of nickel oxide, 35 parts by weight of cobalt oxide, 52 parts by weight of manganese dioxide, 117 parts by weight of lithium carbonate and 6 parts by weight of yttrium oxide are weighed and added into 1000 parts by weight of deionized water to be uniformly stirred, so as to obtain uniform mixed liquid.
2) Adding the mixed solution obtained in the step 1) into a nano sand mill, performing ball milling for 1h, taking out slurry, and performing spray drying at 170 ℃ to obtain yttrium ion modified precursor powder of the ternary cathode material of the lithium ion battery.
3) And (3) performing appropriate briquetting (4MPa) treatment on the powder obtained in the step 2), calcining in an oxygen atmosphere, firstly heating to 550 ℃ and preserving heat for 5h, then heating to 950 ℃ and preserving heat for 8h, and screening through a 200-mesh screen after calcining to obtain the yttrium ion substituted lithium ion battery ternary cathode material (see figure 2).
The phase detection of the ternary positive electrode material for lithium ion batteries prepared above was performed using an X-ray diffractometer (XRD, Rigaku, japan), and the phase detection result is shown in fig. 1. As can be seen from FIG. 1, the material forms a good layered structure, the lithium-nickel mixed phase is low, the R value (003/004) is 1.64, and the tiny new peak is Y2O3Characteristic peak of (2), Y2O3The existence of (2) is beneficial to protecting the stability of the structure and reducing the corrosion of the electrolyte. The XRD pattern (figure 3) after crystal modification confirms that the crystal modification is R-3m space group of hexagonal phase, and the crystal modification result shows that the occupation degree of yttrium ions substituting the position of the transition layer is 0.0041 and meets the theoretical expectation, namely the Li (Ni) is verified0.6Co0.2Mn0.2)0.995Y0.005O2. As can be seen from FIG. 3, the primary particle size is between 900 and 1200nm, and the morphology is uniform.
Uniformly mixing 0.8g of the obtained lithium ion ternary positive electrode material, 0.1g of conductive carbon powder and 0.1g of organic binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, adding 0.05mL of solvent NMP, fully stirring to obtain viscous slurry, uniformly coating the viscous slurry on the surface of an aluminum foil, drying by air blowing, placing in a vacuum drying oven at 120 ℃ for drying for 8 hours, and rolling to obtain the positive electrode plate.
The electrochemical performance of the obtained ternary cathode material was evaluated using a 2016 type half cell. And (3) stamping the rolled battery pole piece into a wafer with the diameter of 12mm, accurately weighing the mass of the wafer, calculating the mass of the ternary positive electrode material in the pole piece according to the formula composition, wherein the diameter of the used diaphragm is 19mm, the diameter of the used negative electrode lithium piece is 15mm, and assembling the wafer into the testable button battery in a Germany Braun glove box.
And (3) carrying out electrochemical performance test on the button cell: as shown in fig. 4, the initial specific discharge capacity at 1C rate is 159.2mAh/g, the capacity retention rate after 100 cycles is 92.2%, and the cycle performance of the material is stable. Has potential commercial application value.
Example 2
An yttrium ion modified lithium ion battery ternary positive electrode material comprises the following raw materials in parts by weight:
nickel oxide: 135 parts of (A);
cobalt oxide: 35 parts of (B);
manganese dioxide: 52 parts of (1);
lithium carbonate: 117 parts of (a);
yttrium oxide: 6 parts.
The preparation process specifically comprises the following steps:
1) 135 parts by weight of nickel oxide, 35 parts by weight of cobalt oxide, 52 parts by weight of manganese dioxide, 117 parts by weight of lithium carbonate and 6 parts by weight of yttrium oxide are weighed and added into 1000 parts by weight of deionized water to be uniformly stirred, so as to obtain uniform mixed liquid.
2) Adding the mixed solution obtained in the step 1) into a nano sand mill, performing ball milling for 1h, taking out slurry, and performing spray drying at 170 ℃ to obtain yttrium ion modified precursor powder of the ternary cathode material of the lithium ion battery.
3) And (3) carrying out appropriate briquetting (4MPa) treatment on the powder obtained in the step 2), calcining in an oxygen atmosphere, firstly heating to 550 ℃, preserving heat for 5h, then heating to 850 ℃, preserving heat for 10h, and sieving through a 200-mesh sieve after calcining is finished to obtain the yttrium ion substituted lithium ion battery ternary cathode material.
The phase detection of the ternary cathode material of the lithium ion battery is carried out by using an X-ray diffractometer (XRD, Rigaku of Japan), and the phase detection result shows that the material forms a good layered structure, the lithium-nickel mixed row is low, the R value (003/004) is 1.57, and the tiny new peak is Y2O3Characteristic peak of (2), Y2O3The existence of (2) is beneficial to protecting the stability of the structure and reducing the corrosion of the electrolyte. The XRD pattern after crystal modification is confirmed to be an R-3m space group of a hexagonal phase, and the crystal modification result shows that the occupancy degree of yttrium ions substituting the position of a transition layer is 0.0039, which accords with the theoretical expectation, namely, Li (Ni) is verified0.6Co0.2Mn0.2)0.995Y0.005O2. The particle size of the material is between 800 and 1100nm, and the shape is uniform.
Example 3
An yttrium ion modified lithium ion battery ternary positive electrode material comprises the following raw materials in parts by weight:
nickel oxide: 135 parts of (A);
cobalt oxide: 35 parts of (B);
manganese dioxide: 52 parts of (1);
lithium carbonate: 117 parts of (a);
yttrium oxide: 6 parts.
The preparation process specifically comprises the following steps:
1) 135 parts by weight of nickel oxide, 35 parts by weight of cobalt oxide, 52 parts by weight of manganese dioxide, 117 parts by weight of lithium carbonate and 6 parts by weight of yttrium oxide are weighed and added into 1000 parts by weight of deionized water to be uniformly stirred, so as to obtain uniform mixed liquid.
2) Adding the mixed solution obtained in the step 1) into a nano sand mill, performing ball milling for 1h, taking out slurry, and performing spray drying at 170 ℃ to obtain precursor powder of the ternary cathode material of the lithium ion battery.
3) And (3) performing appropriate briquetting (4MPa) treatment on the powder obtained in the step 2), calcining in an oxygen atmosphere, firstly heating to 550 ℃ and preserving heat for 5h, then heating to 750 ℃ and preserving heat for 12h, and sieving through a 200-mesh screen after calcining to obtain the yttrium ion substituted lithium ion battery ternary cathode material.
The phase detection of the ternary cathode material of the lithium ion battery is carried out by using an X-ray diffractometer (XRD, Rigaku of Japan), and the phase detection result shows that the material forms a good layered structure, the lithium-nickel mixed row is low, the R value (003/004) is 1.54, and the tiny new peak is Y2O3Characteristic peak of (2), Y2O3The existence of (2) is beneficial to protecting the stability of the structure and reducing the corrosion of the electrolyte. The XRD pattern after crystal modification is confirmed to be an R-3m space group of a hexagonal phase, and the crystal modification result shows that the occupation degree of yttrium ions substituting the position of a transition layer is 0.0042 and accords with theoretical expectation, namely Li (Ni) is verified0.6Co0.2Mn0.2)0.995Y0.005O2. The particle size of the material is between 700 and 1000nm, and the shape is uniform.
Example 4
An yttrium ion modified lithium ion battery ternary positive electrode material comprises the following raw materials in parts by weight:
nickel oxide: 134 parts of a binder;
cobalt oxide: 43 parts of a mixture;
manganese dioxide: 51.5 parts;
lithium carbonate: 117 parts of (a);
yttrium oxide: 11 parts.
The preparation process specifically comprises the following steps:
1) 134 parts by weight of nickel oxide, 43 parts by weight of cobalt oxide, 51.5 parts by weight of manganese dioxide, 117 parts by weight of lithium carbonate and 11 parts by weight of yttrium oxide were weighed and added to 1000 parts by weight of deionized water and stirred uniformly to obtain a uniform mixed solution.
2) Adding the mixed solution obtained in the step 1) into a nano sand mill, performing ball milling for 1h, taking out slurry, and performing spray drying at 170 ℃ to obtain precursor powder of the ternary cathode material of the lithium ion battery.
3) And (3) performing appropriate briquetting (4MPa) treatment on the powder obtained in the step 2), calcining in an oxygen atmosphere, firstly heating to 550 ℃, preserving heat for 5 hours, then heating to 950 ℃, preserving heat for 8 hours, and sieving through a 200-mesh screen after calcining to obtain the yttrium ion substituted lithium ion battery ternary cathode material.
The phase detection of the ternary cathode material of the lithium ion battery is carried out by using an X-ray diffractometer (XRD, Rigaku of Japan), and the phase detection result shows that the material forms a good layered structure, the lithium-nickel mixed row is low, the R value (003/004) is 1.59, and the tiny new peak is Y2O3Characteristic peak of (2), Y2O3The existence of (2) is beneficial to protecting the stability of the structure and reducing the corrosion of the electrolyte. The XRD pattern after crystal modification confirms that the crystal modification is an R-3m space group of a hexagonal phase, and the crystal modification result shows that the occupancy degree of yttrium ions substituting the position of the transition layer is 0.0079 and accords with theoretical expectation, namely Li (Ni) is verified0.6Co0.2Mn0.2)0.99Y0.01O2. The particle size of the material is between 900 and 1200nm, and the shape is uniform.
Example 5
An yttrium ion modified lithium ion battery ternary positive electrode material comprises the following raw materials in parts by weight:
nickel oxide: 134 parts of a binder;
cobalt oxide: 43 parts of a mixture;
manganese dioxide: 51.5 parts;
lithium carbonate: 117 parts of (a);
yttrium oxide: 11 parts of,
The preparation process specifically comprises the following steps:
1) 134 parts by weight of nickel oxide, 43 parts by weight of cobalt oxide, 51.5 parts by weight of manganese dioxide, 117 parts by weight of lithium carbonate and 11 parts by weight of yttrium oxide were weighed and added to 1000 parts by weight of deionized water and stirred uniformly to obtain a uniform mixed solution.
2) Adding the mixed solution obtained in the step 1) into a nano sand mill, performing ball milling for 1h, taking out slurry, and performing spray drying at 170 ℃ to obtain precursor powder of the ternary cathode material of the lithium ion battery.
3) And (3) carrying out appropriate briquetting (4MPa) treatment on the powder obtained in the step 2), calcining in an oxygen atmosphere, firstly heating to 550 ℃, preserving heat for 5h, then heating to 850 ℃, preserving heat for 10h, and sieving through a 200-mesh sieve after calcining is finished to obtain the yttrium ion substituted lithium ion battery ternary cathode material.
The phase detection of the ternary cathode material of the lithium ion battery is carried out by using an X-ray diffractometer (XRD, Rigaku of Japan), and the phase detection result shows that the material forms a good layered structure, the lithium-nickel mixed row is low, the R value (003/004) is 1.59, and the tiny new peak is Y2O3Characteristic peak of (2), Y2O3The existence of (2) is beneficial to protecting the stability of the structure and reducing the corrosion of the electrolyte. The XRD pattern after crystal modification confirms that the crystal modification is R-3m space group of hexagonal phase, and the crystal modification result shows that the occupancy degree of yttrium ions substituting the position of the transition layer is 0.0082 and accords with theoretical expectation, namely the Li (Ni) is verified0.6Co0.2Mn0.2)0.99Y0.01O2. The particle size of the material is between 800 and 1100nm, and the shape is uniform.
Example 6
An yttrium ion modified lithium ion battery ternary positive electrode material comprises the following raw materials in parts by weight:
nickel oxide: 134 parts of a binder;
cobalt oxide: 43 parts of a mixture;
manganese dioxide: 51.5 parts;
lithium carbonate: 117 parts of (a);
yttrium oxide: 11 parts.
The preparation process specifically comprises the following steps:
1) 134 parts by weight of nickel oxide, 43 parts by weight of cobalt oxide, 51.5 parts by weight of manganese dioxide, 117 parts by weight of lithium carbonate and 11 parts by weight of yttrium oxide were weighed and added to 1000 parts by weight of deionized water and stirred uniformly to obtain a uniform mixed solution.
2) Adding the mixed solution obtained in the step 1) into a nano sand mill, performing ball milling for 1h, taking out slurry, and performing spray drying at 170 ℃ to obtain precursor powder of the ternary cathode material of the lithium ion battery.
3) And (3) performing appropriate briquetting (4MPa) treatment on the powder obtained in the step 2), calcining in an oxygen atmosphere, firstly heating to 550 ℃ and preserving heat for 5h, then heating to 750 ℃ and preserving heat for 12h, and sieving through a 200-mesh screen after calcining to obtain the yttrium ion substituted lithium ion battery ternary cathode material.
The phase detection of the ternary cathode material of the lithium ion battery is carried out by using an X-ray diffractometer (XRD, Rigaku of Japan), and the phase detection result shows that the material forms a good layered structure, the lithium-nickel mixed row is low, the R value (003/004) is 1.59, and the tiny new peak is Y2O3Characteristic peak of (2), Y2O3The existence of (2) is beneficial to protecting the stability of the structure and reducing the corrosion of the electrolyte. The XRD pattern after crystal modification confirms that the crystal modification is R-3m space group of hexagonal phase, and the crystal modification result shows that the occupancy degree of yttrium ions substituting the position of the transition layer is 0.0081 and accords with theoretical expectation, namely the Li (Ni) is verified0.6Co0.2Mn0.2)0.99Y0.01O2. The particle size of the material is between 700 and 1000nm, and the shape is uniform.
Example 7
An yttrium ion modified lithium ion battery ternary positive electrode material comprises the following raw materials in parts by weight:
nickel oxide: 133 parts of (A);
cobalt oxide: 41 parts of (1);
manganese dioxide: 51 parts of a mixture;
lithium carbonate: 117 parts of (a);
yttrium oxide: 16 parts of.
The preparation process specifically comprises the following steps:
1) 133 parts by weight of nickel oxide, 41 parts by weight of cobalt oxide, 51 parts by weight of manganese dioxide, 117 parts by weight of lithium carbonate and 16 parts by weight of yttrium oxide were weighed and added to 1000 parts by weight of deionized water and stirred uniformly to obtain a uniform mixed solution.
2) Adding the mixed solution obtained in the step 1) into a nano sand mill, performing ball milling for 1h, taking out slurry, and performing spray drying at 170 ℃ to obtain precursor powder of the ternary cathode material of the lithium ion battery.
3) And (3) performing appropriate briquetting (4MPa) treatment on the powder obtained in the step 2), calcining in an oxygen atmosphere, firstly heating to 550 ℃, preserving heat for 5 hours, then heating to 950 ℃, preserving heat for 8 hours, and sieving through a 200-mesh screen after calcining to obtain the yttrium ion substituted lithium ion battery ternary cathode material.
The phase detection of the ternary cathode material of the lithium ion battery is carried out by using an X-ray diffractometer (XRD, Rigaku of Japan), and the phase detection result shows that the material forms a good layered structure, the lithium-nickel mixed row is low, the R value (003/004) is 1.59, and the tiny new peak is Y2O3Characteristic peak of (2), Y2O3The existence of (2) is beneficial to protecting the stability of the structure and reducing the corrosion of the electrolyte. The XRD pattern after crystal modification is confirmed to be an R-3m space group of a hexagonal phase, and the crystal modification result shows that the occupation degree of yttrium ions substituting the position of the transition layer is 0.0138 and accords with the theoretical expectation, namely Li (Ni) is verified0.6Co0.2Mn0.2)0.985Y0.015O2. The particle size of the material is between 900 and 1100nm, and the shape is uniform.
Example 8
An yttrium ion modified lithium ion battery ternary positive electrode material comprises the following raw materials in parts by weight:
nickel oxide: 133 parts of (A);
cobalt oxide: 41 parts of (1);
manganese dioxide: 51 parts of a mixture;
lithium carbonate: 117 parts of (a);
yttrium oxide: 16 parts of.
The preparation process specifically comprises the following steps:
1) 133 parts by weight of nickel oxide, 41 parts by weight of cobalt oxide, 51 parts by weight of manganese dioxide, 117 parts by weight of lithium carbonate and 16 parts by weight of yttrium oxide were weighed and added to 1000 parts by weight of deionized water and stirred uniformly to obtain a uniform mixed solution.
2) Adding the mixed solution obtained in the step 1) into a nano sand mill, performing ball milling for 1h, taking out slurry, and performing spray drying at 170 ℃ to obtain precursor powder of the ternary cathode material of the lithium ion battery.
3) And (3) carrying out appropriate briquetting (4MPa) treatment on the powder obtained in the step 2), calcining in an oxygen atmosphere, firstly heating to 550 ℃, preserving heat for 5h, then heating to 850 ℃, preserving heat for 10h, and sieving through a 200-mesh sieve after calcining is finished to obtain the yttrium ion substituted lithium ion battery ternary cathode material.
The phase detection of the ternary cathode material of the lithium ion battery is carried out by using an X-ray diffractometer (XRD, Rigaku of Japan) and shows that the material forms a good layered structure, the lithium-nickel mixed row is low, the R value (003/004) is 1.57, and the tiny new peak is Y2O3Characteristic peak of (2), Y2O3The existence of (2) is beneficial to protecting the stability of the structure and reducing the corrosion of the electrolyte. The XRD pattern after crystal modification confirms that the crystal modification is R-3m space group of hexagonal phase, and the crystal modification result shows that the occupation degree of yttrium ions substituting the position of the transition layer is 0.0139, which is in line with theoretical expectation, namely, Li (Ni) is verified0.6Co0.2Mn0.2)0.985Y0.015O2. The particle size of the material is between 900 and 1200nm, and the shape is uniform.
Example 9
An yttrium ion modified lithium ion battery ternary positive electrode material comprises the following raw materials in parts by weight:
nickel oxide: 133 parts of (A);
cobalt oxide: 41 parts of (1);
manganese dioxide: 51 parts of a mixture;
lithium carbonate: 117 parts of (a);
16 parts of yttrium oxide.
The preparation process specifically comprises the following steps:
1) 133 parts by weight of nickel oxide, 41 parts by weight of cobalt oxide, 51 parts by weight of manganese dioxide, 117 parts by weight of lithium carbonate and 16 parts by weight of yttrium oxide were weighed and added to 1000 parts by weight of deionized water and stirred uniformly to obtain a uniform mixed solution.
2) Adding the mixed solution obtained in the step 1) into a nano sand mill, performing ball milling for 1h, taking out slurry, and performing spray drying at 170 ℃ to obtain precursor powder of the ternary cathode material of the lithium ion battery.
3) And (3) performing appropriate briquetting (4MPa) treatment on the powder obtained in the step 2), calcining in an oxygen atmosphere, firstly heating to 550 ℃ and preserving heat for 5h, then heating to 750 ℃ and preserving heat for 12h, and sieving through a 200-mesh screen after calcining to obtain the yttrium ion substituted lithium ion battery ternary cathode material.
The phase detection of the ternary cathode material of the lithium ion battery is carried out by using an X-ray diffractometer (XRD, Rigaku of Japan), and the phase detection result shows that the material forms a good layered structure, the lithium-nickel mixed row is low, the R value (003/004) is 1.61, and the tiny new peak is Y2O3Characteristic peak of (2), Y2O3The existence of (2) is beneficial to protecting the stability of the structure and reducing the corrosion of the electrolyte. The XRD pattern after crystal modification confirms that the crystal modification is R-3m space group of hexagonal phase, and the crystal modification result shows that the occupancy degree of yttrium ions replacing transition layer positions is 0.0141, which is in accordance with theoretical expectation, namely, Li (Ni) is verified0.6Co0.2Mn0.2)0.985Y0.015O2. The particle size of the material is between 1000-1100nm, and the shape is uniform.

Claims (9)

1. An yttrium ion modified lithium ion battery ternary cathode material is characterized in that the chemical formula is Li (Ni)0.6Co0.2Mn0.2)1-xYxO2Wherein x is more than or equal to 0.005 and less than or equal to 0.015.
2. The yttrium ion modified lithium ion battery ternary positive electrode material of claim, wherein x has a value of 0.005, 0.01, or 0.015.
3. The method for preparing the yttrium ion modified lithium ion battery ternary cathode material according to claim 1 or 2, characterized by comprising the following steps:
step 1: weighing 130-136 parts of nickel oxide, 40-46 parts of cobalt oxide, 50-53 parts of manganese dioxide, 117 parts of lithium carbonate and 5-17 parts of yttrium oxide, adding into 1200 parts of deionized water by weight of 900-1200 parts, and uniformly stirring to obtain a uniform mixed solution;
step 2: adding the mixed solution obtained in the step (1) into a nano sand mill, performing ball milling for 30-80min, taking out the slurry, and performing spray drying at the temperature of 160-180 ℃ to obtain precursor powder of the ternary cathode material of the lithium ion battery;
and step 3: and (3) briquetting the powder obtained in the step (2), calcining in an oxygen atmosphere, heating to 400-550 ℃, preserving heat for 5h, heating to 750-950 ℃, preserving heat for 8-12h, and obtaining the yttrium ion modified lithium ion battery ternary cathode material after calcining.
4. The method for preparing the yttrium ion modified lithium ion battery ternary cathode material according to claim 3, wherein when x is 0.005, raw materials in parts by weight are weighed in step 1: 135 parts of nickel oxide, 45 parts of cobalt oxide, 52 parts of manganese dioxide, 117 parts of lithium carbonate and 6 parts of yttrium oxide.
5. The method for preparing the yttrium ion modified lithium ion battery ternary cathode material according to claim 4, wherein the calcination process in the step 3 is as follows: firstly, heating to 400-550 ℃ and preserving heat for 5h, then heating to 950 ℃ and preserving heat for 8h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 850 ℃ and preserving heat for 10h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 750 ℃ and preserving heat for 12h, and ending the calcination.
6. The method for preparing the yttrium ion modified lithium ion battery ternary cathode material according to claim 3, wherein when x is 0.01, raw materials in parts by weight are weighed in step 1: 134 parts of nickel oxide, 43 parts of cobalt oxide, 51.5 parts of manganese dioxide, 117 parts of lithium carbonate and 11 parts of yttrium oxide.
7. The method for preparing the yttrium ion modified lithium ion battery ternary cathode material according to claim 6, wherein the calcination process in the step 3 is as follows: firstly, heating to 400-550 ℃ and preserving heat for 5h, then heating to 950 ℃ and preserving heat for 8h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 850 ℃ and preserving heat for 10h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 750 ℃ and preserving heat for 12h, and ending the calcination.
8. The method for preparing the yttrium ion modified lithium ion battery ternary cathode material according to claim 3, wherein when x is 0.015, raw materials in parts by weight are weighed in step 1: 133 parts of nickel oxide, 41 parts of cobalt oxide, 51 parts of manganese dioxide, 117 parts of lithium carbonate and 16 parts of yttrium oxide.
9. The method for preparing the yttrium ion modified lithium ion battery ternary cathode material according to claim 8, wherein the calcination process in the step 3 is as follows: firstly, heating to 400-550 ℃ and preserving heat for 5h, then heating to 950 ℃ and preserving heat for 8h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 850 ℃ and preserving heat for 10h, and finishing calcination; or firstly heating to 400-550 ℃ and preserving heat for 5h, then heating to 750 ℃ and preserving heat for 12h, and ending the calcination.
CN202010184885.0A 2020-03-17 2020-03-17 Yttrium ion modified lithium ion battery ternary positive electrode material and preparation method thereof Pending CN111342039A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108346798A (en) * 2018-03-23 2018-07-31 复旦大学 The preparation method of doping type nickel-cobalt lithium manganate cathode material
CN109817919A (en) * 2019-01-22 2019-05-28 上海应用技术大学 A kind of ternary cathode material of lithium ion battery and preparation method thereof of rubidium doping

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108346798A (en) * 2018-03-23 2018-07-31 复旦大学 The preparation method of doping type nickel-cobalt lithium manganate cathode material
CN109817919A (en) * 2019-01-22 2019-05-28 上海应用技术大学 A kind of ternary cathode material of lithium ion battery and preparation method thereof of rubidium doping

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