CN111106343A - Lanthanum and fluorine co-doped high-nickel ternary cathode material and preparation method and application thereof - Google Patents

Lanthanum and fluorine co-doped high-nickel ternary cathode material and preparation method and application thereof Download PDF

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CN111106343A
CN111106343A CN201911392283.8A CN201911392283A CN111106343A CN 111106343 A CN111106343 A CN 111106343A CN 201911392283 A CN201911392283 A CN 201911392283A CN 111106343 A CN111106343 A CN 111106343A
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lanthanum
fluorine
nickel
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张震
廖大健
王倩
廖纪军
范文俊
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South China University of Technology SCUT
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Abstract

The invention discloses a lanthanum and fluorine co-doped high-nickel ternary cathode material and a preparation method and application thereof. The preparation method comprises the following steps: preparing a nickel source, a cobalt source and a manganese source into a solution, and adding a precipitator to obtain a precipitate. Then uniformly mixing a lanthanum source, a fluorine source and a precursor in ethanol, evaporating a solvent, mixing the treated precursor with a lithium salt, and synthesizing the lanthanum-fluorine-codoped high-nickel ternary material LiNi through presintering and sintering(0.6‑x)Co0.2Mn0.2LaxO(2‑y)FyA positive electrode material, wherein,0<x<0.03，0<y<0.03. the invention overcomes the defects of poor cycle performance and rate performance of the traditional high-nickel ternary material under high cut-off voltage, has 91.5 percent of capacity retention rate after 150 cycles under the current density of 2C, and has the specific discharge capacity of 139mAh g under the current density of 10C‑1。

Description

Lanthanum and fluorine co-doped high-nickel ternary cathode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a lanthanum and fluorine co-doped high-nickel ternary cathode material as well as a preparation method and application thereof.
Background
High nickel ternary material (LiNi) for lithium ion batteryxCoyMn(1-x-y)O2，x>0.5) has higher working voltage and energy density and longer cycle life, is environment-friendly, and has been widely applied to the field of power batteries at present. In order to meet the demand of power batteries, the nickel content in the ternary material is increasing, which is beneficial for obtaining higher energy density and lower cost, since nickel is cheaper than cobalt. However, a series of problems are also caused when the nickel content in the ternary material becomes high. Due to Li+And Ni2+The ionic radius of the lithium nickel is very close to that of the nickel, and the electrochemical performance of the material is poor due to serious mixed lithium and nickel in the material; residual lithium on the surface of the high-nickel ternary material causes more side reactions between the electrode and the electrolyte in the circulation process, so that the polarization and the interface resistance in the battery are increased, and the surface structure of the electrode is further damaged; and the development of the high-nickel ternary material is hindered to a certain extent due to the defects that the high-nickel ternary material is easy to degrade under high cut-off voltage and is easy to generate phase change in the charging and discharging processes.
Doping modification is one of the main methods for improving the cycle stability and the structural stability of the ternary cathode material. The doping is started from the interior of the material, and the structure of the material is modified to a certain extent, and the doping comprises metal ion and non-metal ion doping. A common doping metal ion is Mg2+、Al3+、Nb5+、Ti4+、Zr4+、La3+Etc. rather than metalsThe ions being predominantly F-And Cl-And (5) ion doping. The doping can reduce the increase of impedance in the charging and discharging process, and better maintain the stability of the ternary structure.
Chinese patent application No. 201910186124.6 discloses an aluminum-doped NCM622 type high-nickel ternary material and a preparation method thereof. During lithium preparation, aluminum hydroxide is added, a precursor and a lithium salt are uniformly mixed, and then the mixture is calcined to obtain an aluminum element doped NCM622 type high-nickel ternary material, and through doping modification, the structural stability of the high-nickel ternary material can be effectively improved, and the rate capability and the cycle performance of the material are improved.
Chinese patent CN201811521420.9 discloses a method for preparing a gradient sintered gas-phase fluorine-doped modified high-nickel cathode material, which comprises sintering a high-nickel material under high-purity fluorine gas by a gradient sintering technique to obtain a target product, but the preparation method cannot accurately control the doping amount of fluorine, and the electrochemical performance of the material is not ideal.
Disclosure of Invention
The invention aims to provide a lanthanum and fluorine co-doped high-nickel ternary cathode material and a preparation method and application thereof in order to prepare a high-nickel ternary material with high specific capacity and stable cycle performance. Lanthanum is used to substitute nickel element to be doped into crystal lattice, and fluorine is used to substitute oxygen element to be doped into crystal lattice, thus forming LiNi(0.6-x)Co0.2Mn0.2LaxO(2-y)FyA positive electrode material, wherein 0<x<0.03，0<y<0.03. Lanthanum ion doped material is used as columnar ion to enlarge c-axis distance and center with positive charge, thereby enhancing Li+And phase transition is suppressed. The introduction of fluorine can enable stronger F-M (M ═ Ni, Co, Mn) bonds to replace O-M bonds, so that the structure of the material is more stable, and the cycle performance of the material is improved.
The purpose of the invention is realized by the following technical scheme.
A lanthanum and fluorine co-doped high-nickel ternary positive electrode material has a chemical formula of LiNi(0.6-x)Co0.2Mn0.2LaxO(2-y)FyWherein, 0<x<0.03，0<y<0.03。
Preferably, the chemical formula of the ternary cathode material is LiNi0.59Co0.2Mn0.2La0.01O1.98F0.02Or LiNi0.58Co0.2Mn0.2La0.02O1.98F0.02。
Preferably, the particle size of the primary particles of the ternary cathode material is 200-700nm, and the primary particles are agglomerated after sintering to form irregular secondary particles.
The preparation method of the lanthanum and fluorine co-doped high-nickel ternary cathode material comprises the following steps:
(1) according to LiNi(0.6-x)Co0.2Mn0.2LaxO(2-y)FyDissolving nickel salt, cobalt salt and manganese salt in water according to the stoichiometric ratio to obtain solution A; weighing a precipitator to prepare a solution B; mixing and stirring the solution A and the solution B, and filtering to obtain a precipitate;
(2) according to LiNi(0.6-x)Co0.2Mn0.2LaxO(2-y)FyWeighing lanthanum salt and villiaumite according to the stoichiometric ratio, dissolving the lanthanum salt and the villiaumite in ethanol, adding the precipitate obtained in the step (1), stirring, heating, evaporating the solvent to dryness, and drying to obtain a precursor;
(3) and (3) fully grinding and mixing the precursor obtained in the step (2) with lithium salt, placing the mixture in a muffle furnace, pre-burning and sintering the mixture in the air to obtain the lanthanum-fluorine co-doped high-nickel ternary cathode material.
Preferably, the precipitating agent in the step (1) is sodium carbonate or sodium oxalate.
Preferably, the stirring time in step (1) is 12 to 15 hours.
Preferably, the lanthanum salt and the fluorine salt in the step (2) are lanthanum nitrate and ammonium fluoride.
Preferably, the stirring time in step (2) is 1 to 3 hours.
Preferably, the lithium salt in step (3) is lithium carbonate or lithium hydroxide.
Preferably, the molar ratio of the precursor to the lithium salt in step (3) is 1:1.03-1: 1.09.
Preferably, the temperature rising rate of the pre-sintering in the step (3) is 3-5 ℃/min, the temperature of the pre-sintering is 400-500 ℃, and the time of the pre-sintering is 4-6 hours.
Preferably, the temperature rise rate of the sintering in the step (3) is 3-5 ℃/min, the sintering temperature is 800-900 ℃, and the sintering time is 12-18 hours.
The lanthanum and fluorine co-doped high-nickel ternary cathode material is applied to the preparation of lithium ion batteries.
Preferably, the specific process of the application is as follows: and mixing the lanthanum and fluorine co-doped high-nickel ternary material, acetylene black and PVDF for pulping, and then coating the mixture on an aluminum foil to obtain the lithium ion battery anode.
Preferably, the lanthanum and fluorine co-doped high-nickel ternary material, the acetylene black and the PVDF are mixed and pulped according to the ratio (mass ratio) of 80:10: 10.
Preferably, the application process is as follows: weighing 0.05g of lanthanum and fluorine co-doped high-nickel ternary material, 0.0062g of PVDF and 0.0062g of acetylene black, mixing and grinding, transferring into a small glass bottle, adding 1mL of NMP, magnetically stirring for 2h, coating the material on an aluminum foil to prepare an electrode, and assembling the electrode in a glove box by taking metal lithium as a counter electrode to form the CR2016 type button cell.
The lanthanum-fluorine co-doped high-nickel ternary positive electrode material is synthesized by a simple method, has excellent electrochemical performance under the condition of high cut-off voltage of 4.6V, and has high initial discharge specific capacity of 176mAh g-1(at a current density of 320mA g-1(2C) Next), and still has a capacity retention of 91.5% after 150 cycles. At 10C (1600mA g)-1) The discharge specific capacity can reach 139mAh g under the current density-1。
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention improves the structural stability of the high-nickel ternary material during charge and discharge under high cut-off voltage. The invention adopts lanthanum and fluorine co-doped high-nickel IIIThe element material, lanthanum ion entering material is used as columnar ion to enlarge the c-axis distance, thereby being beneficial to Li+And phase transition is suppressed. The F-M (M ═ Ni, Co, Mn) bond with stronger bond energy is substituted for O-M bond by fluorine ion to make the structure of the material more stable, and F is negative univalent, and oxygen is negative bivalent, in order to keep the electric neutrality of the material, part of metal ion is reduced (generally Ni is used as negative bivalent)3+Reduction of Ni2+)，Ni3+The increase of the amount of the lithium-nickel mixed can effectively reduce the lithium-nickel mixed row.
(2) The invention reduces the corrosion of the electrolyte to the high-nickel ternary material. Under the combined action of lanthanum nitrate and ammonium fluoride, a small amount of lanthanum fluoride can be formed on the surface of the material in the high-temperature calcination process, and the lanthanum fluoride can reduce the corrosion of electrolyte on the high-nickel ternary material. Under high cut-off voltage, the material can carry out deep lithium removal and lithium insertion, and the synergistic effect of lanthanum and fluorine can enable the structure of the material to be more stable, so that the material has excellent electrochemical performance.
(3) According to the preparation method of the high-nickel ternary material, the lanthanum salt and the villiaumite are dissolved in the ethanol in the step (2), the precursor is added, and then the solvent is evaporated to dryness, so that the lanthanum salt, the villiaumite and the precursor can be mixed very uniformly, co-doping can be completed in one step, the operation is simple and easy to control, and the preparation method is suitable for batch production.
(4) The preparation method is simple in process, safe, nontoxic, green and environment-friendly, and the prepared lanthanum-fluorine co-doped high-nickel ternary material LiNi(0.6-x)Co0.2Mn0.2LaxO(2-y)FyA positive electrode material, wherein 0<x<0.03，0<y<0.03, the layered structure was good (the value of c/a obtained from XRD was larger than 4.96), and the particle size was uniform and was 400-600 nm.
(4) The invention has excellent electrochemical performance under the high charge cut-off voltage of 4.6V, and not only has high initial discharge specific capacity of 176mAh g-1(Current Density 320mA g-1(2C) And still has a capacity retention of 91.5% after 150 cycles. At 10C (1600mA g)-1) The discharge specific capacity can reach 139mAh g under the current density-1。
Drawings
Fig. 1 is an XDR diagram of a positive electrode material prepared in example 4 of the present invention.
FIG. 2 shows that the current density of the positive electrode material prepared in example 4 of the present invention is 320mA g-1Cycle performance graph below.
FIG. 3 is a graph of rate capability of 3-4.6V for the cathode material prepared in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) According to the weight ratio of Ni: co: 7.3408g of nickel acetate, 2.4908g of cobalt acetate and 2.4509g of manganese acetate are weighed according to the molar ratio of Mn to 0.59:0.2:0.2 and dissolved in water, 6.3594g of sodium carbonate is weighed to prepare a solution, the two solutions are mixed and stirred for 12 hours, and precipitate is obtained by filtration.
(2) Lanthanum nitrate and ammonium fluoride are weighed and dissolved in ethanol according to the stoichiometric ratio (nickel acetate: lanthanum nitrate: ammonium fluoride is 0.59:0.01:0.01), then the precipitate obtained in the step (1) is added and stirred for 1 hour, and then the solvent is heated and evaporated to dryness and dried.
(3) And (3) mixing the precursor obtained in the step (2) with lithium salt according to a molar ratio of 1:1.03 fully grinding and mixing, placing the mixture in a muffle furnace, setting the presintering temperature to 400 ℃ and the presintering time to 5 hours and the sintering temperature to 800 ℃ and the sintering time to 12 hours at the heating rate of 3 ℃/min in the air, and naturally cooling to room temperature to obtain the lanthanum-fluorine co-doped high-nickel ternary material LiNi0.59Co0.2Mn0. 2La0.01O1.99F0.01。
0.05g of the positive electrode material in the embodiment, 0.0062g of PVDF and 0.0062g of acetylene black are weighed, mixed and ground, transferred into a small glass bottle, added with 1mL of NMP, magnetically stirred for 2 hours, coated on an aluminum foil to prepare an electrode, assembled into a CR2016 type button cell in a glove box by using metal lithium as a counter electrode, and subjected to electrochemical performance test. The results of the test data obtained are shown in table 1,
example 2
(1) According to the weight ratio of Ni: co: 7.2164g of nickel acetate, 2.4908g of cobalt acetate and 2.4509g of manganese acetate are weighed according to the molar ratio of Mn to 0.58:0.2:0.2 and dissolved in water, 6.3594g of sodium carbonate is weighed to prepare a solution, the two solutions are mixed and stirred for 12 hours, and precipitate is obtained by filtration.
(2) Lanthanum nitrate and ammonium fluoride are weighed according to the stoichiometric ratio (nickel acetate: lanthanum nitrate: ammonium fluoride is 0.58:0.02:0.01), dissolved in ethanol, added with the precipitate obtained in the step (1), stirred for 1 hour, heated to evaporate the solvent to dryness and dried.
(3) And (3) mixing the precursor obtained in the step (2) with lithium salt according to a molar ratio of 1: 1.05, fully grinding and mixing, placing in a muffle furnace, setting the presintering temperature to 400 ℃, the presintering time to 5 hours, the sintering temperature to 800 ℃ and the sintering time to 12 hours at the heating rate of 3 ℃/min in the air, and naturally cooling to room temperature to obtain the lanthanum-fluorine co-doped high-nickel ternary material LiNi0.58Co0.2Mn0. 2La0.02O1.99F0.01。
An electrode and an assembled battery were prepared in the same manner as in example 1. The assembled cell was subjected to electrochemical performance testing. The results of the test data obtained are shown in table 1.
Example 3
(1) According to the weight ratio of Ni: co: in the molar ratio of Mn to 0.57:0.2:0.2, 7.0919g of nickel acetate, 2.4908g of cobalt acetate, and 2.4509g of manganese acetate were dissolved in water, 6.3594g of sodium carbonate was weighed to prepare a solution, and the two solutions were mixed and stirred for 12 hours, and filtered to obtain a precipitate.
(2) Lanthanum nitrate and ammonium fluoride are weighed and dissolved in ethanol according to the stoichiometric ratio (nickel acetate: lanthanum nitrate: ammonium fluoride is 0.57:0.03:0.01), then the precipitate obtained in the step (1) is added and stirred for 1 hour, and then the solvent is heated and evaporated to dryness and dried.
(3) And (3) mixing the precursor obtained in the step (2) with lithium salt according to a molar ratio of 1: 1.05, fully grinding and mixing, placing in a muffle furnace, setting the presintering temperature to 400 ℃, the presintering time to 5 hours, the sintering temperature to 800 ℃ and the sintering time to 12 hours at the temperature rising rate of 5 ℃/min in the air, and naturally cooling to room temperature to obtain the lanthanum-fluorine co-doped high-nickel ternary material LiNi0.57Co0.2Mn0. 2La0.03O1.99F0.01。
An electrode and an assembled battery were prepared in the same manner as in example 1. The assembled cell was subjected to electrochemical performance testing. The results of the test data obtained are shown in table 1.
Example 4
(1) According to the weight ratio of Ni: co: in the molar ratio of Mn to 0.59:0.2:0.2, 7.3408g of nickel acetate, 2.4908g of cobalt acetate, and 2.4509g of manganese acetate were dissolved in water, 6.3594g of sodium carbonate was weighed to prepare a solution, and the two solutions were mixed and stirred for 12 hours, and filtered to obtain a precipitate.
(2) Lanthanum nitrate and ammonium fluoride are weighed and dissolved in ethanol according to the stoichiometric ratio (nickel acetate: lanthanum nitrate: ammonium fluoride is 0.59:0.01:0.02), then the precipitate obtained in the step (1) is added and stirred for 1 hour, and then the solvent is heated and evaporated to dryness and dried.
(3) And (3) mixing the precursor obtained in the step (2) with lithium salt according to a molar ratio of 1:1.03 fully grinding and mixing, placing the mixture in a muffle furnace, setting the presintering temperature to be 450 ℃, the presintering time to be 5 hours, the sintering temperature to be 850 ℃ and the sintering time to be 12 hours at the heating rate of 3 ℃/min in the air, and naturally cooling to room temperature to obtain the lanthanum-fluorine co-doped high-nickel ternary material LiNi0.59Co0.2Mn0. 2La0.01O1.98F0.02。
FIG. 1 is an XDR diagram of the positive electrode material prepared in this example, and the material synthesized as shown in the figure is α -NaFeO2The intensity ratio of the 003 peak to the 104 peak of the layered structure is more than 1.2, which indicates that the material does not have serious lithium-nickel mixed-discharge. An electrode and an assembled battery were prepared in the same manner as in example 1. The assembled cell was subjected to electrochemical performance testing. The results of the test data obtained are shown in fig. 2 and 3. Fig. 2 shows the cycling performance at 2C current density of the cells obtained in example 4 and comparative example 1, with the capacity retention of 91.5% after 150 cycles for the cell obtained in example 4, and only 72.6% for the cell obtained in comparative example 1; FIG. 3 is a graph of rate performance of the batteries obtained in example 4 and comparative example 1, and it can be seen from the graph that the specific capacities of the modified materials at different current densities are significantly improvedLiter, wherein the specific discharge capacity of example 4 was 139mAh g at a 10C high current density-140mAh g higher than that of comparative example 1-1。
Example 5
(1) According to the weight ratio of Ni: co: in the molar ratio of Mn to 0.58:0.2:0.2, 7.2164g of nickel acetate, 2.4908g of cobalt acetate, and 2.4509g of manganese acetate were dissolved in water, 6.3594g of sodium carbonate was weighed to prepare a solution, and the two solutions were mixed and stirred for 12 hours, and filtered to obtain a precipitate.
(2) Lanthanum nitrate and ammonium fluoride are weighed and dissolved in ethanol according to the stoichiometric ratio (nickel acetate: lanthanum nitrate: ammonium fluoride is 0.58:0.01:0.02), then the precipitate obtained in the step (1) is added and stirred for 1 hour, and then the solvent is heated and evaporated to dryness and dried.
(3) And (3) mixing the precursor obtained in the step (2) with lithium salt according to a molar ratio of 1:1.03 fully grinding and mixing, placing the mixture in a muffle furnace, setting the presintering temperature to be 450 ℃, the presintering time to be 5 hours, the sintering temperature to be 850 ℃ and the sintering time to be 15 hours at the heating rate of 3 ℃/min in the air, and naturally cooling to room temperature to obtain the lanthanum-fluorine co-doped high-nickel ternary material LiNi0.58Co0.2Mn0. 2La0.02O1.98F0.02。
An electrode and an assembled battery were prepared in the same manner as in example 1. The assembled cell was subjected to electrochemical performance testing. The results of the test data obtained are shown in table 1.
Comparative example 1
LiNi which is not subjected to doping treatment0.6Co0.2Mn0.2O2The high nickel ternary positive electrode material was subjected to structural testing, and an electrode and an assembled battery were prepared using the same method as in example 1. The assembled cell was subjected to electrochemical performance tests, and the results of the obtained test data are shown in table 2.
Comparative example 2
Lanthanum-doped LiNi0.59Co0.2Mn0.2La0.01O2The high nickel ternary positive electrode material was subjected to structural testing, and an electrode and an assembled battery were prepared using the same method as in example 1. The assembled battery is put intoElectrochemical performance tests are carried out, and the results of the obtained test data are shown in table 2.
TABLE 1
Figure BDA0002345304360000091
TABLE 2
Figure BDA0002345304360000092
Figure BDA0002345304360000101
As can be seen from table 2, compared with the raw material without modification (comparative example 1), the lanthanum-modified high-nickel ternary cathode material (comparative example 2) has obviously improved specific discharge capacity and cycle performance due to the doping of lanthanum ions; from table 1, it can be seen that the introduction of fluoride ion doping based on lanthanum doping further improves the cycling performance of the material, wherein example 4 (LiNi)0.59Co0.2Mn0.2La0.01O1.98F0.02) The highest specific discharge capacity and capacity retention rate are shown.

Claims (10)

1. The lanthanum and fluorine co-doped high-nickel ternary cathode material is characterized in that the chemical formula of the ternary cathode material is LiNi(0.6-x)Co0.2Mn0.2LaxO(2-y)FyWherein, 0<x<0.03，0<y<0.03。
2. The lanthanum and fluorine co-doped high-nickel ternary cathode material as claimed in claim 1, wherein the chemical formula of the ternary cathode material is LiNi0.59Co0.2Mn0.2La0.01O1.98F0.02Or LiNi0.58Co0.2Mn0.2La0.02O1.98F0.02。
3. The method for preparing the lanthanum and fluorine co-doped high-nickel ternary cathode material as claimed in claim 1 or 2, is characterized by comprising the following steps:
(1) according to LiNi(0.6-x)Co0.2Mn0.2LaxO(2-y)FyDissolving nickel salt, cobalt salt and manganese salt in water according to the stoichiometric ratio to obtain solution A; weighing a precipitator to prepare a solution B; mixing and stirring the solution A and the solution B, and filtering to obtain a precipitate;
(2) according to LiNi(0.6-x)Co0.2Mn0.2LaxO(2-y)FyWeighing lanthanum salt and villiaumite according to the stoichiometric ratio, dissolving the lanthanum salt and the villiaumite in ethanol, adding the precipitate obtained in the step (1), stirring, heating, evaporating the solvent to dryness, and drying to obtain a precursor;
(3) and (3) fully grinding and mixing the precursor obtained in the step (2) with lithium salt, placing the mixture in a muffle furnace, pre-burning and sintering the mixture in the air to obtain the lanthanum-fluorine co-doped high-nickel ternary cathode material.
4. The method according to claim 3, wherein the precipitating agent in step (1) is sodium carbonate or sodium oxalate.
5. The method according to claim 3, wherein the lanthanum salt and the fluorine salt in step (2) are lanthanum nitrate and ammonium fluoride.
6. The production method according to claim 3, wherein the stirring time in the step (2) is 1 to 3 hours.
7. The method according to claim 3, wherein the molar ratio of the precursor to the lithium salt in the step (3) is 1:1.03 to 1: 1.09.
8. The preparation method according to claim 3, wherein the temperature increase rate of the pre-sintering in the step (3) is 3-5 ℃/min, the temperature of the pre-sintering is 400-500 ℃, and the time of the pre-sintering is 4-6 hours.
9. The method as claimed in claim 3, wherein the temperature of step (3) is 3-5 ℃/min, the sintering temperature is 800-900 ℃, and the sintering time is 12-18 hours.
10. The lanthanum and fluorine co-doped high-nickel ternary cathode material of claim 1 or 2 is applied to the preparation of a lithium ion battery.
CN201911392283.8A 2019-12-30 2019-12-30 Lanthanum and fluorine co-doped high-nickel ternary cathode material and preparation method and application thereof Pending CN111106343A (en)

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