CN109728275B - Method for improving electrochemical performance of high-nickel ternary cathode material by using scandium fluoride - Google Patents
Method for improving electrochemical performance of high-nickel ternary cathode material by using scandium fluoride Download PDFInfo
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Abstract
The invention relates to a method for improving the electrochemical performance of a high-nickel ternary cathode material by scandium fluoride, belonging to the field of preparation of lithium ion cathode materials. Scandium fluoride prepared from scandium oxide powder, ammonium fluoride and the like is mixed with a high-nickel ternary precursor and a lithium source solid phase, so that the cost is reduced, and ScF is generated on the surface of a high-nickel ternary cathode material3And the existence of F-containing ions inhibits the side reaction of the surface of the high-nickel ternary material and the electrolyte. ScF generated on surface of high-nickel ternary material3And the phase has negative thermal expansion capacity, plays a certain role in inhibiting the volume expansion of the material in the charge and discharge processes of the battery, relieves the problem of structural deterioration caused by volume contraction and expansion, and enhances the stability of the material at high temperature. Through ScF3The multiplying power characteristic and the cycle performance of the coated material are improved. The invention improves the electrochemical performance of the high-nickel ternary cathode material of the lithium ion battery under the heavy current density, and improves the rate characteristic and the cycle performance of the material.
Description
Technical Field
The invention relates to a method for improving the electrochemical performance of a high-nickel ternary cathode material by scandium fluoride, belonging to the field of preparation of lithium ion cathode materials.
Background
With the change of global climate, the greenhouse effect is gradually intensified, the fossil energy crisis is generated, and low carbon life is the inevitable trend of times development. The emission of automobile exhaust in a first-line city is one of the main reasons for air quality deterioration, and the government of China encourages people to buy and use new energy electric automobiles, effectively popularize the application of the new energy electric automobiles and promote the low-carbon life process of the city. Although the demand for new energy electric vehicles is increasing, the acceptance of electric vehicles by the public is still low, mainly due to the short single endurance mileage and the long charging time. In order to meet the requirements of a new energy electric automobile for long single-time driving mileage and short charging time, the development of a high-performance lithium ion battery is urgent. The positive electrode material is a main reason for restricting the development of the lithium ion battery, the rate performance of the positive electrode material directly influences the application of lithium ions in high-power electrical appliances, and the development of the high-rate and high-capacity lithium ion battery positive electrode material is very important.
The nickel cobalt lithium manganate ternary positive electrode material shows better electrochemical performance due to the synergistic effect of Ni-Co-Mn, and becomes one of the most promising positive electrode materials of the lithium ion battery at present. With the increase of the nickel content, the specific capacity of the ternary material is gradually increased, but the phase change of the material in the charging and discharging process is aggravated, the time for completely removing lithium ions from the material is prolonged, the side reaction between the surface of the material and electrolyte is increased, the dissolution of transition metal is aggravated, and the rate characteristic and the cycle stability of the material are deteriorated.
Disclosure of Invention
The invention aims to improve the electrochemical performance of a high-nickel ternary cathode material of a lithium ion battery under high current density, improve the rate characteristic and the cycle performance of the material, and provide a method for improving the electrochemical performance of the high-nickel ternary cathode material by scandium fluoride.
The purpose of the invention is realized by the following technical scheme.
The method for improving the electrochemical performance of the high-nickel ternary cathode material by using scandium fluoride comprises the following specific steps:
step one, mixing scandium oxide powder and ammonium fluoride powder in a ball mill according to a molar ratio of 3:1 to prepare mixed powder A;
step two, heating the powder A obtained in the step one to 300-700 ℃ in Ar gas atmosphere, and calcining for 8-12 h to obtain scandium fluoride powder B;
step three, mixing the powder B obtained in the step two with a high-nickel ternary precursor of the lithium ion battery and a lithium source in a ball mill according to a corresponding ratio for 0.5-1.5 hours to obtain powder C;
step four, heating the powder C obtained in the step three to the temperature of 450-900 ℃ in an oxygen atmosphere, calcining for 10-15 hours at the temperature to obtain a high-nickel ternary positive electrode material, and generating ScF on the surface3。
Step one, the ball milling tank and the ball milling beads are made of zirconia or agate materials;
firstly, the ball milling rotating speed is 50-150 rpm;
step one, the ball milling time is 0.5-1.5 h;
step two, the calcining temperature is 300-700 ℃;
the calcination time in the second step is 8-12 h;
step three, the high nickel ternary precursor is NixCoyMn1-x-y(OH)2Wherein: 0.6 ≦ x ≦ 1;
thirdly, the molar ratio of the precursor to the lithium source is 1: 1.02-1.08;
step three the ScF3The mass ratio of the precursor to the high-nickel ternary precursor is 1-5: 100;
step three, the ball milling tank is made of polytetrafluoroethylene and polyurethane;
step three, the lithium source is lithium carbonate or lithium hydroxide;
step three, the rotating speed of the ball mill is 100-200 rpm;
fourthly, the calcining temperature is 450-900 ℃;
and fourthly, the calcining time is 8-12 hours.
Advantageous effects
1. According to the invention, a certain proportion of powder materials are mixed in the ball mill, so that the uniform mixing of two raw materials is facilitated, and the purity of the prepared material is ensured.
2. The invention is realized by mixing ScF3The high-nickel ternary precursor and the lithium source are simultaneously subjected to ball milling and mixing, so that the cost is reduced, and the material can be uniformly coated on the surface of the high-nickel ternary cathode material after calcination.
3. The invention disperses the material by simple ball milling process, the method is simple and has no pollution to the environment.
4. The method generates the ScF on the surface of the high-nickel ternary cathode material by a simple method3And the existence of F-containing ions inhibits the side reaction of the surface of the high-nickel ternary material and the electrolyte.
5. The invention generates ScF on the surface of the high-nickel ternary material3And the phase has negative thermal expansion capacity, plays a certain role in inhibiting the volume expansion of the material in the charge and discharge process of the battery, relieves the structural deterioration caused by the expansion and contraction of the material in the charge and discharge cycle process, and enhances the stability of the material at high temperature.
Drawings
FIG. 1 shows the high nickel ternary positive electrode material Ni of the lithium ion battery in example 10.9Co0.05Mn0.05(OH)2Coated ScF3SEM images of the material thereafter;
FIG. 2 shows LiNi, a high-nickel ternary positive electrode material for a lithium ion battery of example 10.9Co0.05Mn0.05O2Coated ScF3Front and back XRD patterns;
FIG. 3 shows LiNi, a high-nickel ternary positive electrode material for a lithium ion battery of example 10.9Co0.05Mn0.05O2And (3) charging and discharging cycle curves under the conditions of coating and non-coating of 5C multiplying power of 2.7-4.3V.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings.
Example 1:
the method for improving the electrochemical performance of the high-nickel ternary cathode material by using scandium fluoride comprises the specific steps of
1) 0.8644g of ammonium fluoride and 0.5359g of scandium oxide are subjected to ball milling and mixing on a planetary ball mill in a zirconia ball milling tank, the rotating speed is 100rpm, and the ball milling is carried out for 1 h;
2) heating the powder obtained in the step 1) to 300 ℃ in a tube furnace in an argon atmosphere for 2h, and then heating to 600 ℃ for 8h to obtain ScF3Powder;
3) 0.4886gNi will be mixed0.9Co0.05Mn0.05(OH)2Precursor, 0.2071g of lithium hydroxide, 0.0209g of ScF obtained in step 2)3Adding polyurethane balls into the powder in a polytetrafluoroethylene ball milling tank, and mixing for 1h at the rotating speed of 150 rpm;
4) heating the mixed powder obtained in the step 3) to 700 ℃ in an oxygen atmosphere and keeping the temperature for 12h to obtain ScF3Coated LiNi0.9Co0.05Mn0.05O2The ternary electrode material has an SEM picture shown in figure 1 and an XRD pattern shown in figure 2;
5) assembling the electrode material into a button battery through coating and drying, carrying out constant-current charge-discharge test, and carrying out ScF (non-coated glass) test3LiNi of (2)0.9Co0.05Mn0.05O2Material comparison, ScF3The multiplying power characteristic and the cycle performance of the coated material are improved, the charging and discharging cycle curve of the coated material under the voltage of 2.7-4.3V and the multiplying power of 5C is shown in figure 3, and the coated material is subjected to ScF3The capacity of the coating treatment material still remained 74.5mAh/g after 300 weeks of cycling.
Example 2:
the method for improving the electrochemical performance of the high-nickel ternary cathode material by using scandium fluoride comprises the specific steps of
1) 0.8644g of ammonium fluoride and 0.5359g of scandium oxide are subjected to ball milling and mixing on a planetary ball mill in a zirconia ball milling tank, the rotating speed is 100rpm, and the ball milling is carried out for 1 h;
2) heating the powder obtained in the step 1) to 300 ℃ in a tube furnace in an argon atmosphere for 2h, and then heating to 600 ℃ for 8h to obtain ScF3Powder;
3) 0.4583gNi will be mixed0.8Co0.1Mn0.1(OH)2Precursor, 0.1261g of lithium hydroxide, 0.0138g of ScF obtained in step 2)3Adding polyurethane balls into the powder in a polytetrafluoroethylene ball milling tank, and mixing for 1h at the rotating speed of 150 rpm;
4) heating the mixed powder obtained in the step 3) to 780 ℃ in an oxygen atmosphere and keeping for 12h to obtain ScF3Coated LiNi0.8Co0.1Mn0.1O2A ternary electrode material;
5) assembling the electrode material into a button battery through coating and drying, carrying out constant-current charge-discharge test, and carrying out ScF (non-coated glass) test3LiNi of (2)0.8Co0.1Mn0.1O2Material comparison, ScF3The multiplying power characteristic and the cycle performance of the coated material are improved.
Example 3:
the method for improving the electrochemical performance of the high-nickel ternary cathode material by using scandium fluoride comprises the specific steps of
1) 0.8644g of ammonium fluoride and 0.5359g of scandium oxide are subjected to ball milling and mixing on a planetary ball mill in a zirconia ball milling tank, the rotating speed is 100rpm, and the ball milling is carried out for 1 h;
2) heating the powder obtained in the step 1) to 300 ℃ in a tube furnace in an argon atmosphere for 2h, and then heating to 600 ℃ for 8h to obtain ScF3Powder;
3) 0.4447gNi will be mixed0.6Co0.2Mn0.2(OH)2Precursor, 0.1894g lithium carbonate, 0.0134g ScF from step 2)3Adding polyurethane balls into the powder in a polytetrafluoroethylene ball milling tank, and mixing for 1h at the rotating speed of 150 rpm;
4) heating the mixed powder obtained in the step 3) to 850 ℃ in an oxygen atmosphere and keeping for 12h to obtain ScF3Coated LiNi0.6Co0.2Mn0.2O2A ternary electrode material;
5) assembling the electrode material into a button battery through coating and drying, carrying out constant-current charge-discharge test, and carrying out ScF (non-coated glass) test3LiNi of (2)0.6Co0.2Mn0.2O2Phase of materialThen, through ScF3The multiplying power characteristic and the cycle performance of the coated material are improved.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (1)
1. The method for improving the electrochemical performance of the high-nickel ternary cathode material by using scandium fluoride is characterized by comprising the following steps of: the method comprises the following specific steps:
step one, mixing scandium oxide powder and ammonium fluoride powder in a ball mill according to a molar ratio of 3:1 to prepare mixed powder A;
step two, heating the powder A obtained in the step one to 300-700 ℃ in Ar gas atmosphere, and calcining for 8-12 h to obtain scandium fluoride powder B;
step three, mixing the scandium fluoride powder B obtained in the step two with a high-nickel ternary precursor of the lithium ion battery and a lithium source in a ball mill according to a corresponding proportion for 0.5-1.5 h to obtain powder C;
step four, heating the powder C obtained in the step three to the temperature of 450-900 ℃ in an oxygen atmosphere, calcining for 10-15 hours at the temperature to obtain a high-nickel ternary positive electrode material, and generating ScF on the surface3；
Step three, the high nickel ternary precursor is NixCoyMn1-x-y (OH) 2Wherein: 0.6 ≦ x < 1.
Thirdly, the molar ratio of the high-nickel ternary precursor to the lithium source is 1: 1.02-1.08; thirdly, the mass ratio of the scandium fluoride to the high-nickel ternary precursor is 1-5: 100;
firstly, a ball milling tank and ball milling beads of the ball mill are made of zirconia or agate materials; the rotating speed during ball milling in the first step is 50-150 rpm; in the first step, the ball milling time is 0.5-1.5 h;
thirdly, a ball milling tank of the ball mill is made of polytetrafluoroethylene and polyurethane;
step three, the lithium source is lithium carbonate or lithium hydroxide;
and the rotating speed of the ball mill in the third step is 100-200 rpm.
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