CN108767212B - Lithium ion battery, surface modification ternary material and preparation method - Google Patents

Lithium ion battery, surface modification ternary material and preparation method Download PDF

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CN108767212B
CN108767212B CN201810427930.3A CN201810427930A CN108767212B CN 108767212 B CN108767212 B CN 108767212B CN 201810427930 A CN201810427930 A CN 201810427930A CN 108767212 B CN108767212 B CN 108767212B
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cathode material
ternary cathode
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lithium
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CN108767212A (en
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陈巍
张耀
李鲲
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Xinwangda Power Technology Co ltd
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Sunwoda Electronic Co Ltd
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Abstract

The invention discloses a preparation method of a surface modified ternary cathode material, which comprises the following steps: placing the ternary cathode material pretreated by preset process conditions into an atomic layer deposition reaction chamber filled with a specified atmosphere; triggering a temperature rise program to enable the temperature of the reaction chamber to be in a specified temperature range; vacuumizing the reaction chamber, introducing an organic boron source into the reaction chamber under the action of a carrier gas, and after a first reaction time, continuously introducing the carrier gas to remove the excessive organic boron source to obtain a first precursor of the surface modified ternary cathode material; and introducing a gaseous oxidant into the reaction chamber under the action of the carrier gas, and after controlling the second reaction time of the gaseous oxidant reacting with the first precursor of the surface modification modified ternary cathode material, continuously introducing the carrier gas to remove the excessive gaseous oxidant and reaction byproducts, thereby obtaining the first surface modification modified ternary cathode material coated with the first specified amount of boron oxide.

Description

Lithium ion battery, surface modification ternary material and preparation method
Technical Field
The invention relates to the field of new energy, in particular to a lithium ion battery, a surface modification ternary material and a preparation method thereof.
Background
As a core part of a new energy automobile, the performance of the power type lithium ion battery is directly related to the popularization and the promotion of the new energy automobile, and the performance of the power type lithium ion battery also provides a huge market for the lithium ion battery industry. As an important component of the lithium ion battery, the improvement of the performance of the anode material is of great importance to the improvement of the performance of the lithium ion battery. The ternary positive electrode material gradually expands the market share in the power type lithium ion battery for the new energy automobile by virtue of higher energy density, so that the ternary positive electrode material becomes the focus of attention in the industry at the present stage.
The new energy automobile requires that the power type lithium ion battery for the automobile has high energy density, and also requires that the power type lithium ion battery for the automobile has excellent cycle performance, high-temperature storage performance and the like. Therefore, the power type lithium ion battery of the new energy automobile has high requirements on the cycle life and the storage life of the anode material. Researches show that one main reason influencing the cycle performance and the storage performance of the ternary cathode material is due to the degradation phenomenon of the surface of the ternary cathode material, wherein the degradation phenomenon comprises phase transition of the surface of the ternary cathode material, dissolution of transition metal ions, oxidation of high-valence transition metal ions to electrolyte in a release state, and corrosion of a decomposition product HF of lithium salt to the surface of the ternary cathode material.
For the above degradation phenomenon, an effective improvement effect can be achieved by surface coating modification, but conventional liquid phase coating or solid phase coating cannot make the coating uniformly distributed on the surface of the ternary cathode material, and even the coating is incomplete, the performance of the power lithium ion battery of the ternary cathode material is still affected, so the prior art needs to be improved.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a surface modification ternary cathode material, and aims to solve the technical problem that the conventional coating method cannot enable a coating to be uniformly distributed on the surface of the ternary cathode material.
The invention provides a preparation method of a surface modification ternary cathode material, which comprises the following steps:
placing the ternary cathode material pretreated by preset process conditions into an atomic layer deposition reaction chamber filled with a specified atmosphere;
triggering a temperature rise program to enable the temperature of the reaction chamber to be in a specified temperature range;
vacuumizing the reaction chamber, introducing an organic boron source into the reaction chamber under the action of a carrier gas, and after a first reaction time, continuously introducing the carrier gas to remove the excessive organic boron source to obtain a first precursor of the surface modified ternary cathode material;
and introducing a gaseous oxidant into the reaction chamber under the action of the carrier gas, and after controlling the second reaction time of the gaseous oxidant reacting with the first precursor of the surface modification modified ternary cathode material, continuously introducing the carrier gas to remove the excessive gaseous oxidant and reaction byproducts, thereby obtaining the first surface modification modified ternary cathode material coated with the first specified amount of boron oxide.
Preferably, after the step of introducing a gaseous oxidant into the reaction chamber under the action of the carrier gas, controlling the second reaction time of the reaction between the gaseous oxidant and the first precursor of the surface modified ternary cathode material, and continuing to introduce the carrier gas to remove excess gaseous oxidant and reaction byproducts, so as to obtain the first surface modified ternary cathode material coated with the specified amount of boron oxide, the method further includes:
under the action of the carrier gas, organic lithium salt is introduced into the reaction chamber, after the third reaction time that the specified lithium salt reacts with the boron oxide on the surface of the first surface modified ternary cathode material is controlled, the carrier gas is continuously introduced to remove the excessive organic lithium salt, and a second precursor of the surface modified ternary cathode material is formed;
and introducing a gaseous oxidant into the reaction chamber under the action of the carrier gas, and after controlling the fourth reaction time for the gaseous oxidant to react with the second precursor of the surface modified ternary cathode material, continuously introducing the carrier gas to remove the excessive gaseous oxidant and reaction byproducts, thereby obtaining a second surface modified ternary cathode material coated with a second specified amount of lithium boron oxide.
Preferably, the organic boron source comprises one or more of trimethyl borane, triethyl borane, diborane and boron trichloride.
Preferably, the gaseous oxidant comprises oxygen and/or H2O。
Preferably, the carrier gas comprises nitrogen and/or argon.
Preferably, the organic lithium salt comprises an alkyl lithium.
Preferably, the alkyl lithium comprises one or more of methyl lithium, propyl lithium, butyl lithium, ethyl lithium and phenyl lithium.
Preferably, the preset process conditions include drying at a temperature ranging from 100 ℃ to 150 ℃ for 6h to 12 h; the specified temperature range comprises 100 ℃ to 200 ℃; the first reaction time comprises 0.1s to 6 s; the second reaction time comprises 0.05s to 20 s; the first reaction time comprises 0.1s to 6 s.
The invention also provides a surface modification ternary cathode material, which is prepared by the preparation method of the surface modification ternary cathode material; comprises a ternary material matrix and a boride coating layer coated on the surface of the ternary material matrix and having a nano-scale thickness range; the nanoscale thickness range includes 0.5nm to 2 nm.
The invention also provides a lithium ion battery, which comprises the surface modification ternary cathode material prepared by the preparation method of the surface modification ternary cathode material.
The invention has the beneficial technical effects that: according to the invention, the ternary cathode material taking three transition metal elements of nickel, cobalt and manganese as main elements is coated with the boron compound by an atomic deposition method, so that the boron compound can be uniformly coated on the surface of the ternary cathode material, the thickness is extremely thin and reaches the nanometer level, and the lithium ions in the charging and discharging process can be ensured to be separated from and embedded into the surface interface of the ternary cathode material; the thickness of the boron compound coating layer is controllable, the coating layer is complete, the protection effect of the boron compound coating layer on the surface of the anode material can be better exerted, and the direct contact between the surface of the ternary anode material and electrolyte is reduced, so that the comprehensive performances such as the stability, the processing performance and the like of the ternary anode material are improved, the performances of a power type lithium ion battery taking the ternary anode material as an anode active material are further improved, and particularly the long-term electrochemical performances such as the cycle performance and the storage performance are improved.
Drawings
FIG. 1 is an SEM image of a surface modified ternary cathode material according to an embodiment of the present invention;
fig. 2 is a cycle performance diagram of a lithium ion battery corresponding to the surface modified ternary cathode material according to an embodiment of the present invention;
fig. 3 is a graph showing the variation of the capacity retention rate at 60 ℃ of a lithium ion battery corresponding to the surface-modified ternary cathode material according to an embodiment of the present invention;
fig. 4 is a graph showing the change of volume expansion rate at 60 ℃ of a lithium ion battery corresponding to the surface modified ternary cathode material according to an embodiment of the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation method of the surface modification modified ternary cathode material provided by the embodiment of the invention comprises the following steps:
s1: and placing the ternary cathode material pretreated by the preset process condition into an atomic layer deposition reaction chamber filled with a specified atmosphere.
The ternary positive electrode material takes three transition metal elements of nickel, cobalt and manganese as main elements, and the general formula is LiNixCoyMnzO2(0≤x,y,z<1). The morphology of the ternary cathode material of the present embodiment includes a single crystal morphology or a secondary particle morphology.
The preset process conditions of this embodiment include: drying for 6 to 12 hours at the temperature of between 100 and 150 ℃ so as to sufficiently remove the moisture of the ternary cathode material, improve the surface coating effect of the ternary cathode material and reduce byproducts of the coating process. The specified atmosphere of this embodiment includes dry air to ensure that the moisture content of the ternary cathode material is not affected when the ternary cathode material is placed in the atomic layer deposition reaction chamber.
S2: and triggering a temperature rise program to enable the temperature of the reaction chamber to be in a specified temperature range.
In this embodiment, after the dry ternary cathode material is placed in the ald reaction chamber, the temperature of the ald reaction chamber is enabled to meet the temperature requirement of the cladding reaction by triggering a temperature-raising program. The specified temperature range of the embodiment includes 100 ℃ to 200 ℃, and after the temperature in the reaction chamber reaches the specified temperature range, the reaction chamber is vacuumized for 10s to 20s to purify the coating reaction environment, reduce the occurrence of side reactions and improve the purity of the coating product.
S3: and after the reaction chamber is vacuumized, introducing an organic boron source into the reaction chamber under the action of a carrier gas, and after a first reaction time, continuously introducing the carrier gas to remove the excessive organic boron source to obtain a first precursor of the surface modified ternary cathode material.
The carrier gas of the embodiment comprises high-purity nitrogen and/or argon, and the organic boron source comprises one or more of trimethyl borane, triethyl borane, diborane and boron trichloride. The boron content in the cladding layer is controlled by mixing the organoboron source with a carrier gas to form a carrier gas stream containing a specified amount of organoboron source and controlling the content of organoboron source in the carrier gas stream. The organoboron source of this example is a high purity reagent of analytical grade or higher. The first reaction time of the embodiment includes 0.1s to 6s, the organic boron source reacts under the vacuum condition in the temperature range of 100 ℃ to 200 ℃, so that the organic boron source is bonded with H, O element on the surface of the ternary cathode material in the form of boron atoms and is attached to the surface of the ternary cathode material; the cleaning time for removing the excessive organic boron source (namely the organic boron source which cannot be attached to the surface of the ternary cathode material) by the carrier gas is 3s to 50s, so that the phase purity of the coating layer is improved.
S4: and introducing a gaseous oxidant into the reaction chamber under the action of the carrier gas, and after controlling the second reaction time of the gaseous oxidant reacting with the first precursor of the surface modification modified ternary cathode material, continuously introducing the carrier gas to remove the excessive gaseous oxidant and reaction byproducts, thereby obtaining the first surface modification modified ternary cathode material coated with the first specified amount of boron oxide.
This example then mixes the gaseous oxidant, which includes oxygen and/or H, with a carrier gas to form a carrier gas stream containing a specified concentration of gaseous oxidant2O, molecular-grade dispersed H of high purity is preferred in this example2O to promote uniform distribution of the coating layer. The gaseous oxidant reacts with boron atoms attached to the surface of the ternary cathode material under the action of the carrier gasAnd carrying out oxidation-reduction reaction to generate corresponding boron oxide under the vacuum condition within the temperature range of 100-200 ℃, wherein the second reaction time is 0.05-20 s, and then cleaning the boron oxide by carrier gas for 5-80 s to obtain the first surface modified ternary cathode material coated with the first specified amount of boron oxide.
In another embodiment of the present invention, after step S4, the method further includes:
s5: and under the action of the carrier gas, introducing an organic lithium salt into the reaction chamber, controlling the third reaction time of the reaction between the specified lithium salt and the boric oxide on the surface of the first surface modified ternary cathode material, and then continuously introducing the carrier gas to remove the excessive organic lithium salt to form a second precursor of the surface modified ternary cathode material.
In this embodiment, an organic lithium salt is continuously introduced into the reaction chamber under the action of a carrier gas, so that the organic lithium salt and the boron oxide undergo a chemical reaction to generate a lithium boron oxide under a vacuum condition at a temperature ranging from 100 ℃ to 200 ℃, the third reaction time ranges from 0.1s to 6s, and then the lithium boron oxide is washed by the carrier gas for 3s to 50s, so as to obtain a second surface modified ternary cathode material coated with a second specified amount of lithium boron oxide. The organic lithium salt in this embodiment includes alkyl lithium, and the preferred alkyl lithium in this embodiment includes one or more of methyl lithium, propyl lithium, butyl lithium, ethyl lithium, and phenyl lithium. In the embodiment, the coated lithium boron oxide has a certain lithium ion conductivity, so that the ionic conductivity of the ternary cathode material is further improved, and the electrochemical performance of the lithium ion battery is improved.
S6: and introducing a gaseous oxidant into the reaction chamber under the action of the carrier gas, and after controlling the fourth reaction time for the gaseous oxidant to react with the second precursor of the surface modified ternary cathode material, continuously introducing the carrier gas to remove the excessive gaseous oxidant and reaction byproducts, thereby obtaining a second surface modified ternary cathode material coated with a second specified amount of lithium boron oxide.
This example then mixes the gaseous oxidant, which includes oxygen and/or H, with a carrier gas to form a carrier gas stream containing a specified concentration of gaseous oxidant2O, thisExamples high purity molecular grade dispersed H is preferred2O to promote uniform distribution of the coating layer. And (3) carrying out redox reaction on the gaseous oxidant and the boron oxide and lithium atoms attached to the surface of the ternary cathode material under the action of the carrier gas at the temperature of 100-200 ℃ in vacuum to generate corresponding lithium boron oxide, wherein the fourth reaction time is 0.05-20 s, and then cleaning for 5-80 s by the carrier gas to obtain the first surface modified ternary cathode material coated with the first specified amount of boron oxide.
In another embodiment of the present invention, a carrier gas flow of a gaseous oxidant and a carrier gas flow of an organic lithium salt can be simultaneously and respectively introduced into the reaction chamber to obtain a second surface modified and modified ternary cathode material coated with a second specified amount of lithium boron oxide, so as to save reaction time and reaction cost.
In another embodiment of the present invention, the coating effect of the ternary cathode material surface coated with the boron oxide is optimized by repeating the steps S1 to S4 for a plurality of times; or repeating the steps S1 to S6 for multiple times to optimize the coating effect of the lithium boron oxide coated on the surface of the ternary cathode material. In other embodiments of the present invention, after the lithium boron oxide is repeatedly coated, the operation of adding the organic lithium salt is repeated again, so as to promote the uniform distribution of the lithium boron oxide in the coating layer. Other embodiments of the present invention may repeatedly coat the lithium boron oxide by changing the operations of coating the lithium boron oxide and adding the organic lithium salt, so that the lithium boron oxide may present a gradient distribution in the coating layer, for example, the lithium boron oxide at the outermost side of the coating layer has the largest concentration ratio. In this embodiment, the above steps S1 to S6 are repeated 5 times to obtain an optimized surface modified ternary cathode material with a lithium boron oxide coated on the surface of the ternary cathode material, an SEM image of which is shown in fig. 1, wherein the lithium boron oxide coated on the surface is uniformly distributed on the surface of the ternary cathode material, and the thickness of the coated layer is 2nm or less, so that the surface morphology of the coated composite ternary material is similar to the appearance morphology of the original ternary cathode material.
The invention also provides a surface modification ternary cathode material, which is prepared by the preparation method of the surface modification ternary cathode material; comprises a ternary material matrix and a boride coating layer coated on the surface of the ternary material matrix and having a nano-scale thickness range; the nanoscale thickness range includes 0.5nm to 2 nm.
The invention also provides a lithium ion battery, which comprises the surface modification ternary cathode material prepared by the preparation method of the surface modification ternary cathode material; the mass ratio range of the surface modification modified ternary positive electrode material, the conductive agent and the binder is 92-96: 2-6.
The coating process of the surface modification ternary cathode material of the embodiment of the invention is as follows:
drying the ternary cathode material at the temperature of between 100 and 150 ℃ for 6 to 12 hours, then placing the ternary cathode material into an atomic layer deposition reaction chamber filled with dry air in advance, raising the temperature of the reaction chamber to keep the temperature of the reaction chamber between 100 and 200 ℃, and vacuumizing the reaction chamber for 10 to 20 seconds; nitrogen and/or argon are used as carriers and an organic boron source to form a carrier fluid containing the organic boron source with the specified concentration, the carrier fluid is introduced into the reaction chamber, the reaction time is controlled to be 0.1s to 6s, and the carriers are continuously introduced to clean for 3s to 50s after the reaction is finished; then mixing the gaseous oxidant and carrier gas into carrier gas flow containing the gaseous oxidant with the designated concentration, introducing the carrier gas flow into the reaction chamber, controlling the reaction time to be 0.05 s-20 s, and continuously introducing the carrier gas to clean for 5 s-80 s after the reaction is finished; continuously mixing organic lithium salt and carrier gas to form carrier gas flow containing organic lithium salt with specified concentration, introducing the carrier gas flow into the reaction chamber, controlling the reaction time to be 0.1 s-6 s, and continuously introducing the carrier gas to clean for 3 s-50 s after the reaction is finished; and finally, mixing a gaseous oxidant and a carrier gas to form a carrier gas flow containing the gaseous oxidant with a specified concentration, introducing the carrier gas flow into the reaction chamber, controlling the reaction time to be 0.05-20 s, continuously introducing the carrier gas to clean for 5-80 s after the reaction is finished, obtaining the surface modified ternary anode material coated with the lithium boron oxide, and repeating the coating steps for a specified number of times (when the boron oxide is coated, only the coating step of coating the boron oxide needs to be repeated), so as to obtain the surface modified ternary anode material coated with the lithium boron oxide, wherein the coating amount is preset and the coating layer thickness is preset.
The specific embodiment is as follows:
example 1
Reacting LiNi0.84Co0.1Mn0.06O2Drying at 120 ℃ for 10h, placing the reaction product into an atomic layer deposition reaction chamber filled with dry air in advance, raising the temperature of the reaction chamber to keep the temperature at 150 ℃, and vacuumizing the reaction chamber for 10 s; nitrogen is taken as a carrier to form a carrier fluid with trimethyl borane, the carrier fluid is introduced into the reaction chamber, the reaction time is controlled to be 1s, and nitrogen is continuously introduced to clean the reaction chamber for 10s after the reaction is finished; then H is introduced2Mixing O and nitrogen to form carrier gas flow, introducing the carrier gas flow into the reaction chamber, controlling the reaction time for 1s, and continuously introducing nitrogen to clean for 8s after the reaction is finished; continuously mixing butyl lithium and nitrogen to form carrier gas flow, introducing the carrier gas flow into the reaction chamber, controlling the reaction time to be 2s, and continuously introducing nitrogen to clean the reaction chamber for 10s after the reaction is finished; finally, H is put2Mixing O and nitrogen to form carrier gas flow, introducing the carrier gas flow into the reaction chamber, controlling the reaction time for 1s, continuously introducing nitrogen to clean for 8s after the reaction is finished to obtain the surface modification ternary cathode material coated with the lithium boron oxide, and repeating the coating step for 5 times in sequence to obtain the surface modification ternary cathode material A coated with the lithium boron oxide with the coating thickness of about 1.0nm, as shown in figure 1.
Preparing anode slurry from the surface modification modified ternary anode material A, a conductive agent and a binder according to a mass ratio of 94:3:3, coating, drying and tabletting to prepare a button lithium ion battery A1 and a soft package lithium ion battery A2; the button type lithium ion battery A1 has a discharge rate of 0.1C (theoretical gram capacity calculated by 200 mAh/g) and a gram capacity of 205mAh/g within a voltage range of 2.8-4.25V. The electrical property test result of the soft package lithium ion battery A2 is that, under 50% SOC, the direct current internal resistance is: 13.5m Ω; at 25 ℃, the cycle can be 2100 times (the capacity retention rate is 80%); the cycle performance can be cycled for 1500 times (the capacity retention rate is 80%) at 45 ℃, and is shown in figure 2; can be cycled for 900 times (the capacity retention rate is 80%) at 60 ℃; at 60 ℃, the capacity retention rate is higher than 80% after the full storage of 4.2V for 12 months, and the change curve of the capacity retention rate at 60 ℃ is shown in figure 3; the volume expansion was less than 20% when the sample was fully stored at 4.2V for 90 days at 60 ℃ and the curve of the change in volume expansion rate at 60 ℃ is shown in FIG. 4.
Example 2
The ternary material is LiNi0.6Co0.2Mn0.2O2The drying condition of (A) is 120 ℃/12 h; the temperature of the reaction chamber is 120 ℃; vacuumizing for 20 s; the organic boron source is triethyl borane, the reaction time is 4s, and the cleaning time is 20 s; introduction of H2The post-O reaction time is 0.05s, and the cleaning time is 0.5 s; the organic lithium salt is ethyl lithium, the reaction time is 4s, and the cleaning time is 50 s; introduction of H2The post-O reaction time is 0.05s, and the cleaning time is 0.5 s; and repeating the coating step for 6 times, and obtaining the surface modified ternary cathode material B in the same way as in the example 1, wherein the thickness of the coating layer is 1.2nm, and the coating layer corresponds to a button lithium ion battery B1 and a soft package lithium ion battery B2.
The gram capacity of the button type lithium ion battery B1 can reach 177 mAh/g. The electrical property test result of the soft package lithium ion battery B2 is that, under 50% SOC, the direct current internal resistance is: 13.9m Ω; the product can be cycled 4200 times at 25 ℃ (the capacity retention rate is 80%); circulation can be carried out 3100 times (the capacity retention rate is 80%) at 45 ℃; the product can be cycled for 200 times (the capacity retention rate is 80%) at 60 ℃; at 60 ℃, the full storage is carried out for 15 months at 4.2V, and the capacity retention rate is higher than 80%; full storage at 60 ℃ at 4.2V for 100 days with a volume expansion of less than 20%.
Example 3
The ternary material is LiNi0.33Co0.33Mn0.33O2The drying condition of (2) is 140 ℃/8 h; the temperature of the reaction chamber is 140 ℃; vacuumizing for 16 s; the organic boron source is diborane, the reaction time is 0.1s, and the cleaning time is 3 s; introduction of H2The post-O reaction time is 5s, and the cleaning time is 10 s; the organic lithium salt step is omitted; and repeating the step of coating the boron oxide for 20 times, and obtaining the surface modified ternary cathode material C with the coating thickness of 2.0nm corresponding to the button lithium ion battery C1 and the soft package lithium ion battery C2 in the same way as in the example 1.
The gram capacity of the button type lithium ion battery C1 can reach 145 mAh/g. The electrical property test result of the soft package lithium ion battery C2 is that, under 50% SOC, the direct current internal resistance is: 12.7m Ω; at 25 ℃, the cycle can be 5900 times (the capacity retention rate is 80%); the product can be cycled for 4700 times (the capacity retention rate is 80%) at 45 ℃; the circulation can be carried out 3500 times (the capacity retention rate is 80%) at 60 ℃; at 60 ℃, the full storage is carried out at 4.2V for 25 months, and the capacity retention rate is higher than 80%; at 60 ℃, the full storage at 4.2V for 210 days has volume expansion less than 20%.
Example 4
The ternary material is LiNi0.5Co0.2Mn0.3O2The drying condition of (1) is 130 ℃/10 h; the temperature of the reaction chamber is 200 ℃; vacuumizing for 14 s; the organic boron source is trimethyl borane, the reaction time is 2s, and the cleaning time is 35 s; introduction of H2The post-O reaction time is 20s, and the cleaning time is 20 s; the organic lithium salt is butyl lithium, the reaction time is 0.1s, and the cleaning time is 3 s; introduction of H2The post-O reaction time is 20s, and the cleaning time is 20 s; and repeating the coating step for 5 times, and obtaining the surface modified ternary cathode material D with the coating thickness of 0.5nm corresponding to the button lithium ion battery D1 and the soft package lithium ion battery D2 by using the method otherwise as in the example 1.
The gram capacity of the button type lithium ion battery D1 can reach 166 mAh/g. The electrical property test result of the soft package lithium ion battery D2 is that, under 50% SOC, the direct current internal resistance is: 15.4m Ω; can be cycled 5000 times (the capacity retention rate is 80%) at 25 ℃; at 45 ℃, 3700 times of circulation can be carried out (the capacity retention rate is 80%); the cycle can be 2600 times (the capacity retention rate is 80%) at 60 ℃; at 60 ℃, the full storage is carried out at 4.2V for 17 months, and the capacity retention rate is higher than 80%; at 60 ℃, the full storage at 4.2V for 140 days, the volume expansion is less than 20%.
Example 5
The ternary material is LiNi0.83Co0.1Mn0.07O2The drying condition of (A) is 150 ℃/6 h; the temperature of the reaction chamber is 160 ℃; vacuumizing for 12 s; the organic boron source is boron trichloride, the reaction time is 6s, and the cleaning time is 50 s; introduction of H2The post-O reaction time is 10s, and the cleaning time is 80 s; the organic lithium salt is phenyl lithium, the reaction time is 6s, and the cleaning time is 30 s; introduction of H2The post-O reaction time is 10s, and the cleaning time is 80 s; and repeating the coating step for 3 times, and obtaining the surface modified ternary cathode material E with the coating thickness of 0.8nm corresponding to the button lithium ion battery E1 and the soft package lithium ion battery E2 in the same way as in the example 1.
The gram capacity of the button type lithium ion battery E1 can reach 208 mAh/g. The electrical property test result of the soft package lithium ion battery E2 is that, under 50% SOC, the direct current internal resistance is: 14.3m Ω; can be cycled for 2200 times (the capacity retention rate is 80%) at 25 ℃; can be cycled for 1600 times (the capacity retention rate is 80%) at 45 ℃; the product can be cycled for 1000 times (the capacity retention rate is 80%) at 60 ℃; at 60 ℃, the full storage is carried out for 13 months at 4.2V, and the capacity retention rate is higher than 80%; full storage at 60 ℃ at 4.2V for 90 days, with a volume expansion of less than 20%.
Example 6
The ternary material is LiNi0.5Co0.2Mn0.3O2The drying condition of (A) is 100 ℃/8 h; the temperature of the reaction chamber is 180 ℃; vacuumizing for 15 s; the carrier gas is a mixture of nitrogen and argon, the organic boron source is trimethyl borane, the reaction time is 3s, and the cleaning time is 40 s; introduction of H2The post-O reaction time is 0.05s, and the cleaning time is 30 s; the organic lithium salt is propyl lithium, the reaction time is 0.8s, and the cleaning time is 15 s; introduction of H2The post-O reaction time is 0.05s, and the cleaning time is 30 s; the coating step is not repeated, and the other steps are the same as the example 1, so that the surface modification modified ternary cathode material F is obtained, the coating thickness is 0.7nm, the mass ratio of the surface modification modified ternary cathode material F to the conductive agent to the binder is 92:2:6, and the button type lithium ion battery F1 and the soft package lithium ion battery F2 correspond to each other.
The gram capacity of the button type lithium ion battery F1 can reach 166 mAh/g. The electrical property test result of the soft package lithium ion battery F2 is that, under 50% SOC, the direct current internal resistance is: 15.6 m.OMEGA.; the product can be cycled for 4800 times (the capacity retention rate is 80%) at 25 ℃; 3600 times of circulation (capacity retention rate is 80%) at 45 ℃; at 60 ℃, the cycle can be 2500 times (the capacity retention rate is 80%); at 60 ℃, the full storage at 4.2V is carried out for 18 months, and the capacity retention rate is higher than 80%; at 60 ℃, the full storage at 4.2V for 140 days, the volume expansion is less than 20%.
Example 7
The ternary material is LiNi0.5Co0.2Mn0.3O2The drying condition of (1) is 110 ℃/10 h; the temperature of the reaction chamber is 100 ℃; vacuumizing for 18 s; the organic boron source is trimethyl borane, the reaction time is 0.5s, and the cleaning time is 30 s; the oxidant is oxygen and H2O mixture, introducing oxygen and H2The reaction time after O was 0.35s,the cleaning time is 60 s; the organic lithium salt is methyl lithium, the reaction time is 1.5s, and the cleaning time is 25 s; the oxidant is oxygen and H2O mixture, introducing oxygen and H2The post-O reaction time is 0.35s, and the cleaning time is 60 s; and repeating the coating step for 3 times, otherwise, obtaining the surface modification ternary cathode material G in the same way as the example 1, wherein the thickness of the coating layer is 1.1nm, the mass ratio of the surface modification ternary cathode material G to the conductive agent to the binder is 96:2:2, and the surface modification ternary cathode material G corresponds to the button type lithium ion battery G1 and the soft package lithium ion battery G2.
The gram capacity of the button type lithium ion battery G1 can reach 167 mAh/G. The electrical property test result of the soft package lithium ion battery G2 is that, under 50% SOC, the direct current internal resistance is: 14.4m Ω; at 25 ℃, 4600 times can be circulated (the capacity retention rate is 80%); the circulation can be carried out 3500 times (the capacity retention rate is 80%) at the temperature of 45 ℃; can be cycled 2400 times (the capacity retention rate is 80%) at 60 ℃; at 60 ℃, the full storage at 4.2V is carried out for 18 months, and the capacity retention rate is higher than 80%; at 60 ℃, the full storage at 4.2V is 150 days, and the volume expansion is less than 20 percent.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (9)

1. A preparation method of a surface modified ternary cathode material is characterized by comprising the following steps:
placing the ternary cathode material pretreated by preset process conditions into an atomic layer deposition reaction chamber filled with a specified atmosphere; triggering a temperature rise program to enable the temperature of the reaction chamber to be in a specified temperature range; vacuumizing the reaction chamber, introducing an organic boron source into the reaction chamber under the action of a carrier gas, and after a first reaction time, continuously introducing the carrier gas to remove the excessive organic boron source to obtain a first precursor of the surface modified ternary cathode material;
introducing a gaseous oxidant into the reaction chamber under the action of the carrier gas, and after controlling the second reaction time of the gaseous oxidant reacting with the first precursor of the surface modification modified ternary cathode material, continuously introducing the carrier gas to remove the excessive gaseous oxidant and reaction byproducts, so as to obtain a first surface modification modified ternary cathode material coated with a first specified amount of boron oxide;
under the action of the carrier gas, organic lithium salt is introduced into the reaction chamber, after the third reaction time that the specified lithium salt reacts with the boron oxide on the surface of the first surface modified ternary cathode material is controlled, the carrier gas is continuously introduced to remove the excessive organic lithium salt, and a second precursor of the surface modified ternary cathode material is formed;
and introducing a gaseous oxidant into the reaction chamber under the action of the carrier gas, and after controlling the fourth reaction time for the gaseous oxidant to react with the second precursor of the surface modified ternary cathode material, continuously introducing the carrier gas to remove the excessive gaseous oxidant and reaction byproducts, thereby obtaining a second surface modified ternary cathode material coated with a second specified amount of lithium boron oxide.
2. The preparation method of the surface modification ternary cathode material according to claim 1, wherein the organic boron source comprises one or more of trimethyl borane, triethyl borane and diborane.
3. The method for preparing the surface-modified ternary cathode material according to claim 1, wherein the gaseous oxidant comprises oxygen and/or H2O。
4. The method for preparing the surface-modified ternary cathode material according to claim 1, wherein the carrier gas comprises nitrogen and/or argon.
5. The method for preparing the surface-modified ternary positive electrode material according to claim 1, wherein the organic lithium salt comprises an alkyl lithium.
6. The method for preparing the surface modified ternary cathode material according to claim 5, wherein the alkyl lithium comprises one or more of methyl lithium, propyl lithium, butyl lithium, ethyl lithium and phenyl lithium.
7. The method for preparing the surface modified ternary cathode material according to claim 1, wherein the preset process conditions include drying at a temperature ranging from 100 ℃ to 150 ℃ for 6h to 12 h; the specified temperature range comprises 100 ℃ to 200 ℃; the first reaction time comprises 0.1s to 6 s; the second reaction time comprises 0.05s to 20 s; the third reaction time comprises 0.1s to 6 s.
8. A surface modification ternary cathode material, which is characterized by being prepared by the preparation method of the surface modification ternary cathode material in any one of claims 1 to 7; comprises a ternary material matrix and a boride coating layer coated on the surface of the ternary material matrix and having a nano-scale thickness range; the nanoscale thickness range includes 0.5nm to 2 nm.
9. A lithium ion battery is characterized in that the surface modification ternary cathode material is prepared by the preparation method of the surface modification ternary cathode material according to any one of claims 1 to 7.
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