CN114613988B - Preparation method of high-stability ternary cathode material, ternary cathode material and lithium ion battery - Google Patents
Preparation method of high-stability ternary cathode material, ternary cathode material and lithium ion battery Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 229910013184 LiBO Inorganic materials 0.000 claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 claims abstract description 10
- 238000007664 blowing Methods 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 238000009423 ventilation Methods 0.000 claims abstract description 9
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010453 quartz Substances 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000010405 anode material Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910013716 LiNi Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 36
- 238000005086 pumping Methods 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 239000011247 coating layer Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 10
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 5
- 239000012496 blank sample Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910006561 Li—F Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
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- 229910052723 transition metal Inorganic materials 0.000 description 4
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- 239000012071 phase Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910006715 Li—O Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
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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
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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
- 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
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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
- H01M4/52—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of a high-stability ternary cathode material, the ternary cathode material and a lithium ion battery; the preparation method comprises the following steps: placing the ternary cathode material into a plasma generator, vacuumizing a cavity of the plasma generator, introducing boron fluoride dry gas, blowing the ternary cathode material in a container to a suspension state, and simultaneously starting the plasma generator to generate plasma to bombard the ternary cathode material; stopping ventilation after bombardment for a period of time, pumping out gas, and standing to obtain a high-stability ternary cathode material; the positive electrode material is prepared by the preparation method; the lithium ion battery comprises the high-stability ternary cathode material obtained by the preparation method; the material of the invention is not corroded by HF in electrolyte, reduces capacity attenuation, improves the cycle performance of the material, and can form uniform LiBO 2 And the coating layer enhances the ionic conductivity of the interface.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a preparation method of a high-stability ternary anode material, the ternary anode material and a lithium ion battery.
Background
Energy crisis and energy safety are the serious examinations faced by all countries in the world at present, and the realization of energy diversification is the inevitable choice of national development by improving the energy structure. Because the lithium ion battery has the advantages of high voltage, high specific energy, good cycle performance, little environmental pollution and the like, the lithium ion battery is a key direction for the development of new energy industries of various countries at present. The lithium ion anode material is an important component of the lithium ion battery and is also a key point of the performance of the lithium ion battery.
A Nickel Cobalt Manganese (NCM) ternary cathode material is a material integrating the performances of lithium cobaltate, lithium nickelate and lithium manganate. The NCM ternary positive electrode material has the characteristics of high specific capacity, long cycle life, low toxicity, low price and the like, and three elements of the NCM have good synergistic effect, so the NCM ternary positive electrode material is the most widely applied material at present. The problems of the conventional ternary cathode material are also outstanding, partial oxygen is removed in the charging and discharging process, an irreversible rock salt phase NiO is formed on the surface of the material, and the reversible capacity is attenuated; under the condition of high voltage, the side reaction of the material surface and the electrolyte is intensified, so that the phase change of the material structure is caused, the circulation stability and the safety performance of the battery are reduced, and the development of the ternary material in the direction of the power battery is not facilitated.
In order to improve the cycling stability of ternary positive electrode materials, there are generally several modification methods: optimization of synthesis process, doping and coating, and particularly doping, coating and modification are particularly important. At present, solid-phase high-temperature sintering doping is mostly adopted for doping, and the process has uneven doping and poor controllability. The coating is solid-phase and liquid-phase coating, the coating obtained by the solid-phase coating method is poor in uniformity, the binding force between the coating and the matrix is weak, and the coating is cracked due to anisotropic volume expansion of the anode material in the circulating process, so that the material is continuously deteriorated, and the circulating performance of the material is influenced. Most of liquid phase methods adopt water as a solvent, and the ternary cathode material can cause lithium loss after being washed by water, so that the capacity of the material is reduced finally. Based on the defects of the ternary cathode material, the invention provides a preparation method of a high-stability ternary cathode material, the ternary cathode material and a lithium ion battery.
Disclosure of Invention
The invention aims to provide a preparation method of a high-stability ternary cathode material, the ternary cathode material and a lithium ion battery, and solves the problem of doping and coating at present.
The invention is realized in such a way that the preparation method of the high-stability ternary cathode material comprises the following steps:
s1: putting the ternary anode material into a plasma generator, and then vacuumizing the cavity of the plasma generator;
s2: introducing dry gas into the plasma generator, blowing the ternary cathode material in the container to a suspension state, simultaneously starting the plasma generator, and adjusting power to generate plasma to bombard the ternary cathode material; the drying gas is boron fluoride;
s3: and after the ternary cathode material is bombarded by the plasma for a period of time, stopping ventilation, extracting gas, and standing to obtain the high-stability ternary cathode material.
The invention provides a preparation method of a high-stability ternary cathode material, since F - Has electronegativity greater than O 2- The surface of the ternary anode material forms more stable Li-F bonds and transition metal M-F bonds, so that the structural stability of the surface of the material is improved, the material is protected from being corroded by HF in electrolyte, the capacity attenuation is reduced, the cycle performance of the material is improved, and meanwhile, B 3+ The LiBO and residual lithium on the surface of the ternary cathode material form uniform LiBO 2 The coating layer enhances the ionic conductivity of the interface of the ternary cathode material, and the doping coating is simultaneously realized on the surface of the ternary cathode material in a gas-solid reaction mode, so that the structural stability of the surface of the material is improved, the material is protected from being corroded by HF in electrolyte, the capacity attenuation is reduced, the cycle performance of the material is improved, and the ionic conductivity of the material interface is enhanced.
Preferably, in the step S1, the ternary cathode material is placed in a quartz tube with a one-way seal, the quartz tube is placed in a plasma generator cavity and fixed, the opening of the quartz tube faces outward, a vacuum pump is turned on, and the plasma generator cavity is vacuumized to a vacuum degree of 0 to-0.1 Mpa.
Preferably, the chemical formula of the ternary cathode material in step S1 is LiNi x Co y Mn z O 2 Wherein x is more than or equal to 0.6 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.2, z is more than or equal to 0.1 and less than or equal to 0.2, and x + y + z = 1.
Preferably, the container in step S1 is a one-way sealed quartz tube.
Preferably, the introduction speed of the drying gas in the step S2 is 5-20L/Min, and the time for the plasma to bombard the ternary cathode material is 5-40 minutes.
Preferably, the power of the plasma generator in the step S3 is 100-300W.
Preferably, the high-stability ternary cathode material can be obtained after the step S3 is kept stand for 1-15 minutes.
The other technical scheme of the invention is as follows: the high-stability ternary cathode material is prepared by the preparation method.
Preferably, the high-stability ternary cathode material is LiBO with surface F ion doping 2 A coated ternary positive electrode material.
The other technical scheme of the invention is as follows: a lithium ion battery comprises the high-stability ternary cathode material obtained by the preparation method.
The invention has the beneficial effects that: the Li-F bond and the transition metal M-F bond on the surface of the high-stability ternary cathode material obtained by the preparation method improve the structural stability of the surface of the material, protect the material from being corroded by HF in electrolyte, reduce capacity attenuation, improve the cycle performance of the material, and B 3+ The LiBO and residual lithium on the surface of the ternary cathode material form uniform LiBO 2 A coating layer for enhancing the ionic conductivity of the interface;
introducing gaseous BF by adopting plasma surface treatment 3 Bombarding ternary positive electrode material in gaseous BF 3 The surface treatment is carried out on the ternary cathode material in the plasma atmosphere, and F can be carried out on the surface of the ternary cathode material - Doping with F - Has electronegativity greater than O 2- The surface of the ternary anode material forms more stable Li-F bonds and transition metal M-F bonds, so that the structural stability of the surface of the material is improved, the material is protected from being corroded by HF in electrolyte, the capacity attenuation is reduced, the cycle performance of the material is improved, and meanwhile, B 3+ The LiBO and residual lithium on the surface of the ternary cathode material form uniform LiBO 2 Coating layer for enhancing ion conductivity of its interface, pass through, etcThe bombardment time of the plasma can effectively regulate and control the doping depth and the thickness of the cladding layer;
the high-stability ternary cathode material prepared by the preparation method disclosed by the invention is obviously improved in cycle stability and rate capability.
Drawings
FIG. 1 is a scanning electron microscope image of the ternary cathode material with high stability obtained in example 1 of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1:
a preparation method of a high-stability ternary cathode material comprises the following steps:
s1, mixing 80g of ternary cathode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 Placing the quartz tube into a quartz tube with a one-way seal, placing the quartz tube into a cavity of a plasma generator and fixing the quartz tube, opening the quartz tube outwards, opening a vacuum pump, and pumping the cavity of the plasma generator to a vacuum degree of 0 Mpa;
s2, continuously introducing dry gas BF into the cavity of the plasma generator 3 Blowing the anode material in the quartz tube to a suspension state at the speed of 5L/min, starting a plasma generator at the same time, and adjusting the power to 120W to generate plasma so that the ternary anode material is continuously bombarded by the plasma;
s3, after bombarding the ternary cathode material by the plasma for 5 minutes, stopping ventilation, extracting the gas, and standing for 3 minutes to obtain a surface F - Doped, LiBO 2 And (3) a coated high-stability ternary cathode material, as shown in figure 1.
Example 2:
a preparation method of a high-stability ternary cathode material comprises the following steps:
s1, mixing 80g of ternary cathode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 Placing the quartz tube into a quartz tube with a one-way seal, placing the quartz tube into a cavity of a plasma generator and fixing the quartz tube, opening the quartz tube outwards, opening a vacuum pump, and pumping the cavity of the plasma generator to a vacuum degree of 0 Mpa;
s2, continuously introducing dry gas BF into the cavity of the plasma generator 3 Blowing the anode material in the quartz tube to a suspension state at the speed of 5L/min, starting a plasma generator at the same time, and adjusting the power to 120W to generate plasma so that the ternary anode material is continuously bombarded by the plasma;
s3, after bombarding the ternary cathode material by the plasma for 10 minutes, stopping ventilation, extracting the gas, and standing for 3 minutes to obtain a surface F - Doped, LiBO 2 And (3) a coated high-stability ternary cathode material.
Example 3:
a preparation method of a high-stability ternary cathode material comprises the following steps:
s1, mixing 80g of ternary cathode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 Placing the quartz tube into a quartz tube with a one-way seal, placing the quartz tube into a cavity of a plasma generator and fixing the quartz tube, opening the quartz tube outwards, opening a vacuum pump, and pumping the cavity of the plasma generator to a vacuum degree of 0 Mpa;
s2, continuously introducing dry gas BF into the cavity of the plasma generator 3 Blowing the anode material in the quartz tube to a suspension state at the speed of 5L/min, starting a plasma generator at the same time, and adjusting the power to 120W to generate plasma so that the ternary anode material is continuously bombarded by the plasma;
s3, after bombarding the ternary cathode material by the plasma for 20 minutes, stopping ventilation, extracting the gas, and standing for 3 minutes to obtain a surface F - Doped, LiBO 2 And (3) a coated high-stability ternary cathode material.
Example 4:
a preparation method of a high-stability ternary cathode material comprises the following steps:
s1, mixing 80g of ternary cathode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 Placing the quartz tube into a quartz tube with a one-way seal, placing the quartz tube into a cavity of a plasma generator and fixing the quartz tube, opening the quartz tube outwards, opening a vacuum pump, and pumping the cavity of the plasma generator to a vacuum degree of 0 Mpa;
s2, continuously introducing dry gas BF into the cavity of the plasma generator 3 Blowing the anode material in the quartz tube to a suspension state at the speed of 5L/min, starting a plasma generator at the same time, and adjusting the power to 120W to generate plasma so that the ternary anode material is continuously bombarded by the plasma;
s3, after bombarding the ternary anode material by plasma for 40 minutes, stopping ventilation, extracting gas, and standing for 3 minutes to obtain a surface F - Doped, LiBO 2 And (3) a coated high-stability ternary cathode material.
Example 5:
a preparation method of a high-stability ternary cathode material comprises the following steps:
s1, mixing 60g of ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Placing the quartz tube into a quartz tube with a one-way seal, placing the quartz tube into a cavity of a plasma generator, fixing the quartz tube, opening the quartz tube outwards, opening a vacuum pump, and pumping the cavity of the plasma generator to a vacuum degree of-0.1 Mpa;
s2, continuously introducing dry gas BF into the cavity of the plasma generator 3 Blowing the anode material in the quartz tube to a suspension state at the speed of 20L/min, starting a plasma generator at the same time, and adjusting the power to 240W to generate plasma so that the ternary anode material is continuously bombarded by the plasma;
s3, after bombarding the ternary cathode material by the plasma for 15 minutes, stopping ventilation, extracting the gas, and standing for 5 minutes to obtain a surface F - Doped, LiBO 2 High stability of the coatingAnd (3) a meta-anode material.
Example 6:
a preparation method of a high-stability ternary cathode material comprises the following steps:
s1, mixing 60g of ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Placing the quartz tube into a quartz tube with a one-way seal, placing the quartz tube into a cavity of a plasma generator, fixing the quartz tube, opening the quartz tube outwards, opening a vacuum pump, and pumping the cavity of the plasma generator to a vacuum degree of-0.1 Mpa;
s2, continuously introducing dry gas BF into the cavity of the plasma generator 3 Blowing the anode material in the quartz tube to a suspension state at the speed of 20L/min, starting a plasma generator at the same time, and adjusting the power to 300W to generate plasma so that the ternary anode material is continuously bombarded by the plasma;
s3, after bombarding the ternary cathode material by the plasma for 25 minutes, stopping ventilation, extracting the gas, and standing for 5 minutes to obtain a surface F - Doped, LiBO 2 And (3) a coated high-stability ternary cathode material.
Assembling the half cell: the high-stability ternary cathode material prepared in the embodiment is slurried and coated with acetylene black and PVDF according to the mass ratio of 90:5:5, then the high-stability ternary cathode material is cut into 1 × 1 pole pieces, a metal lithium piece is used as a cathode to assemble a CR2032 button cell, and the prepared button cell is subjected to charge and discharge tests at the normal temperature under the condition of 3.0-4.3V cut-off voltage and 1C multiplying power.
TABLE 1 electrochemical Properties of the examples and blanks
| Positive electrodeMaterial | 1C first discharge capacity (mAh/g) | Discharge capacity (mAh/g) after 100 cycles | Capacity retention ratio after 100 cycles% | |
| Blank sample | LiNi 0.6 Co 0.2 Mn 0.2 O 2 | 164 | 137.5 | 83.8 |
| Example 1 | LiNi 0.6 Co 0.2 Mn 0.2 O 2 | 166 | 152.3 | 91.7 |
| Example 2 | LiNi 0.6 Co 0.2 Mn 0.2 O 2 | 164.5 | 154.8 | 94.1 |
| Example 3 | LiNi 0.6 Co 0.2 Mn 0.2 O 2 | 162.1 | 151.1 | 93.2 |
| Example 4 | LiNi 0.6 Co 0.2 Mn 0.2 O 2 | 159.3 | 144.5 | 90.7 |
| Blank sample | LiNi 0.8 Co 0.1 Mn 0.1 O 2 | 185.6 | 146.4 | 78.9 |
| Example 5 | LiNi 0.8 Co 0.1 Mn 0.1 O 2 | 186.1 | 159.6 | 85.7 |
| Example 6 | LiNi 0.8 Co 0.1 Mn 0.1 O 2 | 184.3 | 162.7 | 88.3 |
Note: blank sample: the ternary positive electrode material is not subjected to surface treatment; cycle retention rate = (100 weeks 1C discharge capacity/first week 1C discharge capacity) × 100%; examples 1 to 4 only change BF 3 And bombarding the ternary cathode material for a certain time.
It can be seen from Table 1 that with BF 3 The initial discharge capacity of the material is obviously reduced by the increase of the time for bombarding the ternary cathode material, but the capacity retention rate of the material is better, and compared with a blank sample, the cycling stability and the like of the material subjected to surface treatment are obviously improved. Due to F - Electrical negative ratio of 2- Macro, with Li + The bond energy of the combined Li-F bond is greater than that of the Li-O bond, F - After doping, add Li + The difficulty of de-intercalation reduces the first discharge capacity of the anode material, but the structural stability of the material is enhanced, and the cycle performance is improved because of F - The bond energy of the M-F bond formed in combination with the transition metal M is also larger than that of the M-O bond. The proper amount of doped F can promote the sintering of the material and make the structure of the anode material more stable, thereby improving the charge-discharge cycle performance, but if the content of the doped F is too much, a new unstable interface can be formed, and the stability of the structure and the electrochemical performance of the material are reduced. It can also be seen from the data in Table 1 that following BF 3 The cycle retention of the material is increased and then decreased when the ternary cathode material is bombarded. Compared with a blank sample, the ternary material in the same type in the examples 1, 2 and 5 has obviously improved cycle performance and improved first discharge capacity, although F - After doping, add Li + The difficulty of de-intercalation can cause the first discharge capacity of the anode material to be reduced, but the surface of the material is simultaneously coated with a layer of uniform fast ion conductor LiBO 2 The coating layer enhances the ionic conductivity of the material interface, and the rate capability of the material is improved, so that the 1C first discharge capacity of the material is also improved.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A preparation method of a high-stability ternary cathode material is characterized by comprising the following steps: the preparation method comprises the following steps:
s1: putting the ternary anode material into a plasma generator, and then vacuumizing the cavity of the plasma generator;
s2: introducing dry gas into the plasma generator, blowing the ternary cathode material in the container to a suspension state, simultaneously starting the plasma generator, and adjusting power to generate plasma to bombard the ternary cathode material; the drying gas is boron fluoride;
s3: after the ternary cathode material is bombarded by the plasma for a period of time, stopping ventilation, extracting gas, and standing to obtain the high-stability ternary cathode material;
in the step S1, the ternary positive electrode material is placed in a quartz tube with a one-way seal, and then the quartz tube is placed in a plasma generator;
in the step S2, the introduction speed of the drying gas is 5-20L/Min, and the time for the plasma to bombard the ternary cathode material is 5-40 minutes;
in the step S3, the power of the plasma generator is 100-300W;
the high-stability ternary cathode material is LiBO with surface F ion doped 2 A coated ternary positive electrode material.
2. The method for preparing the high-stability ternary cathode material according to claim 1, wherein the method comprises the following steps: the vacuum degree in the step S1 is 0-0.1 Mpa.
3. The method for preparing the high-stability ternary cathode material according to claim 1, wherein the method comprises the following steps: the chemical formula of the ternary cathode material in the step S1 is LiNi x Co y Mn z O 2 Wherein x is more than or equal to 0.6 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.2, z is more than or equal to 0.1 and less than or equal to 0.2, and x + y + z = 1.
4. The preparation method of the high-stability ternary cathode material according to claim 1, wherein the preparation method comprises the following steps: and S3 standing for 1-15 minutes to obtain the high-stability ternary cathode material.
5. A high-stability ternary cathode material is characterized in that: the high-stability ternary cathode material is prepared by the preparation method of any one of claims 1 to 4.
6. A lithium ion battery, characterized by: the lithium ion battery comprises the high-stability ternary cathode material obtained by the preparation method of any one of claims 1 to 4.
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