CN112952067B - Preparation method of yttrium oxide graphene modified nickel cobalt lithium manganate composite material for lithium ion battery and prepared composite material - Google Patents
Preparation method of yttrium oxide graphene modified nickel cobalt lithium manganate composite material for lithium ion battery and prepared composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a yttrium oxide graphene modified nickel cobalt lithium manganate composite material for a lithium ion battery, which is provided based on the technical problem that the existing ternary cathode material is poor in high-temperature and high-voltage electrical property. The invention also provides the yttrium oxide graphene modified nickel cobalt lithium manganate composite material prepared by the preparation method. According to the invention, the alcohol solution containing graphene oxide and the aqueous solution containing yttrium ions are mixed with the ternary cathode material, and the alcohol solution containing graphene oxide and the aqueous solution containing yttrium are coated on the surface of the ternary cathode material in a heat treatment manner, so that spherical core-shell structure particles formed by coating the nickel cobalt lithium manganate with yttrium oxide/graphene are prepared, an integral coating layer is formed, the high-temperature and high-voltage electrical property of the nickel cobalt lithium manganate ternary cathode material is improved, and the safety performance is further improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a yttrium oxide graphene modified nickel cobalt lithium manganate composite material for a lithium ion battery and the prepared composite material.
Background
The lithium ion secondary battery has high voltage, high energy density, good cycle performance, low self-discharge rate, no pollution, low production cost, recyclability, etc., so that it is widely used in mobile phones, notebook computers, video cameras, various portable electric tools, electronic instruments, etc. and has become an internationally recognized "green battery". Becomes the key point of the development of all countries in the world in the field of new energy materials.
Lithium ion batteries are the preferred power source for small electronic devices such as mobile communication devices, notebook computers and cameras due to their advantages of high operating voltage (greater than 3 v compared to lithium metal), high specific energy, low self-discharge rate, no memory effect, and excellent cycling stability. Relay lithium cobaltate (LiCoO)2) Lithium nickelate (LiNiO)2) Lithium manganate (LiMn)2O4) And lithium iron phosphate (LiFePO)4) Are used as positive electrode materials of lithium ion batteries. Among them, LiCoO2The cost is high, the price is expensive, the resources are poor, and the toxicity is high; LiNiO2The preparation is difficult. Poor thermal stability and safety; LiMn2O4Although the safety performance is good, the capacity attenuation is obvious, and the cycle reversibility is poor; olivine-type crystalline-structure LiFePO4The conductivity is low, and the theoretical capacity can not be exerted. While lithium ion secondary batteries are widely used as energy sources for various electronic devices, their performance is increasingly required. For example, in order to meet the requirements of some special working occasions, the lithium ion secondary battery is required to be capable of not only performing normal charging and discharging in a high-temperature (55 ℃) environment and a low-temperature (minus 40 ℃) environment, but also required to have a higher initial capacity so as to ensure a relatively long service life. However, the conventional lithium ion secondary battery often cannot achieve good electrochemical performance at both high and low temperatures. Therefore, the need for developing a lithium ion secondary battery having good electrochemical performance in a severe environment is urgent.
The layered nickel-cobalt-manganese ternary cathode material has received much attention because of its advantages such as higher specific energy, good cycle stability, safety, low toxicity and low cost. At present, the ternary cathode material at home and abroad is mainly secondary spherical particles formed by agglomeration of fine primary particles. The secondary spherical particles have the following application problems: 1) the secondary ball structure causes the structural firmness of the skeleton to be poor, and the secondary ball is easy to break under the high compaction condition, so that the particles in the material are exposed, the side reaction is increased, the dissolution of metal ions is intensified, and the electrical performance, particularly the service life, is reduced; 2) the primary particle size of the inner part and the outer part of the secondary ball is small, the structural defects are many, and structural collapse is easy to occur under the high-voltage charging and discharging conditions; 3) the interior of the secondary spherical particles is difficult to coat, and interface side reaction is difficult to inhibit in the high-voltage charging and discharging process, so that the material structure is damaged; 4) the secondary particle material is easy to generate serious gas generation phenomenon, and meanwhile, the high-voltage safety performance is poor. The ternary anode material is made into a single crystal-like shape, so that the problems of high-temperature circulation, storage and the like of the material in the using process, particularly under high voltage, can be effectively solved. In addition, the single-crystal-like material has the following advantages: 1) the processing performance is excellent, the material is not easy to break after the pole piece is rolled, the compaction density is higher, and the volume energy density is higher; 2) the special single particle has large specific surface area, small particle size and high dynamic activity; 3) the surface of the single crystal particle is smooth, the contact with a conductive agent is good, and the transmission of lithium ions is facilitated.
According to the method for coating the surface of the ternary cathode material, the side reaction of electrolyte and the cathode material is reduced to a certain extent by a coating material, the cycle performance and the thermal stability of the material are improved, but the effect is limited, and negative effects are brought at the same time, because the coated metal oxide is an inert material, for example, patent CN111354926A discloses a nickel cobalt lithium manganate composite material and a preparation method thereof, in the preparation process, yttrium oxide nanoparticles and a single crystal nickel cobalt lithium manganate material are calcined to prepare the coated nickel cobalt lithium manganate composite material, and the transmission of lithium ions and electrons is inhibited.
Although the ternary system of the lithium ion battery has higher energy density and is most widely applied to power batteries, in practical application, the ternary system of the lithium ion battery still has the defects of poor conductivity, overlarge resistance and excessive heat generation. The positive electrode needs to have good conductivity to improve its electron transport efficiency, thereby ensuring its small internal resistance and low heat generation. Then, it is important to develop a high-performance positive electrode that can be stably and industrially produced while ensuring that the energy density of the battery is not reduced. Disclosure of Invention
The invention aims to solve the technical problems of poor high-temperature high-voltage electrical property and poor safety performance of the conventional ternary cathode material.
The invention solves the technical problems through the following technical means:
a preparation method for a lithium ion battery comprises the following steps:
(1) ultrasonically dispersing 0.05-0.5g of graphene oxide in 100mL of ethanol solvent for 10-90min to obtain an alcoholic solution containing the graphene oxide; yttrium oxide graphene modified nickel cobalt lithium manganate composite material
(2) Dissolving soluble yttrium inorganic salt in 100mL of water to prepare yttrium water solution with the mass fraction of 1-10%;
(3) dropwise adding the yttrium aqueous solution prepared in the step (2) into a precipitator with the concentration of 0.1-0.5mol/L under the stirring condition, uniformly mixing, then adding the graphene oxide-containing alcoholic solution prepared in the step (1), stirring for 1-30min by a magnetic stirrer with the stirring speed of 50-1000rpm, adding a sodium hydroxide solution to adjust the pH value of a reaction system to be not less than 7.5, reacting for 0.5-2h under the water bath condition of 50-100 ℃, then adding a surface modifier, and aging for 10-48h to prepare a mixed solution;
(4) mixing the mixed solution prepared in the step (3) with a nickel cobalt lithium manganate ternary material, uniformly stirring and mixing, filtering, and drying to obtain surface modified powder;
(5) and (4) carrying out heat treatment on the powder subjected to surface modification prepared in the step (4), wherein the heat treatment temperature is 300-800 ℃, and the heat treatment time is 1-10h, so as to prepare the nano yttrium oxide graphene modified nickel cobalt lithium manganate composite material.
Compared with the traditional method for directly coating the ternary cathode material with the inert material, the method adopts an in-situ coating process and a high-temperature post-treatment process, and coats the nickel cobalt lithium manganate ternary cathode material core to form a surface modification layer.
Preferably, the soluble yttrium inorganic salt in step (2) comprises yttrium-containing hydrochloride or yttrium-containing nitrate.
Preferably, the precipitant in step (3) includes one or more of bicarbonate, acetate, carbonate and oxalate.
Preferably, the ratio of the yttrium aqueous solution to the precipitating agent in the step (3) is 1-10: 1.
Preferably, the surface modifier in the step (3) comprises tetraethoxysilane or methyl orthosilicate.
Preferably, the mass of the surface modifier in the step (3) is 0.01-0.5 wt% of the mass of the yttrium aqueous solution.
Preferably, the core of the nickel cobalt lithium manganate ternary material in the step (4) is LiNixCoyMn(1-x-y)O2Wherein x is more than or equal to 0.6, y is more than 0 and less than or equal to 0.4, and 1-x-y is more than 0; the particle size of the nickel cobalt lithium manganate ternary material is 3.5 mu m.
Preferably, the mass ratio of the nickel cobalt lithium manganate ternary material to the mixed solution in the step (4) is 100: 1-10.
Preferably, the heat treatment in step (5) is performed in an air or oxygen atmosphere.
The invention also provides the yttrium oxide graphene modified nickel cobalt lithium manganate composite material prepared by the preparation method.
The invention has the following beneficial effects:
1. compared with the traditional method for directly coating the ternary cathode material with the inert material, the method adopts an in-situ coating process and a high-temperature post-treatment process, and coats the nickel cobalt lithium manganate ternary cathode material core to form a surface modification layer.
When the prepared yttrium oxide graphene modified nickel cobalt lithium manganate composite material is used for a lithium ion battery, the positive electrode material is high in lithium ion and electron conductivity and good in electrochemical performance, so that the lithium ion battery has high specific capacity and long service life.
Drawings
Fig. 1 is an SEM image of a nano yttrium oxide graphene-modified lithium nickel cobalt manganese oxide composite material prepared in an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings and the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of a yttrium oxide graphene modified nickel cobalt lithium manganate composite material for a lithium ion battery comprises the following steps:
(1) ultrasonically dispersing 0.1g of graphene oxide in 100mL of ethanol solvent for 30min to obtain an alcoholic solution containing the graphene oxide;
(2) dissolving yttrium nitrate in 100mL of water to prepare an yttrium water solution with the mass fraction of 5 wt%;
(3) dropwise adding the yttrium aqueous solution prepared in the step (2) into sodium bicarbonate with the concentration of 0.1mol/L under the stirring condition, uniformly mixing, then adding the graphene oxide-containing alcoholic solution prepared in the step (1), stirring for 3min at 500rpm of a magnetic stirrer, adding a sodium hydroxide solution to adjust the pH value of a reaction system to be more than 8.0, reacting for 1h under the water bath condition of 60 ℃, then adding a surface modifier, and aging for 12h to prepare a mixed solution;
(4) the particle diameter D is adjusted according to the mass ratio of 100:550LiNi of 5 μm0.7Co0.1Mn0.2O2Mixing the ternary material with the mixed solution prepared in the step (3), uniformly stirring and mixing, filtering and drying to prepare surface-modified powder;
(5) and (4) carrying out heat treatment on the powder subjected to surface modification in the step (4) at 500 ℃ for 6h to obtain the nano yttrium oxide graphene modified nickel cobalt lithium manganate composite material.
Example 2
A preparation method of a yttrium oxide graphene modified nickel cobalt lithium manganate composite material for a lithium ion battery comprises the following steps:
(1) ultrasonically dispersing 0.15g of graphene oxide in 100mL of ethanol solvent for 30min to obtain an alcoholic solution containing the graphene oxide;
(2) dissolving yttrium nitrate in 100mL of water to prepare an yttrium water solution with the mass fraction of 5 wt%;
(3) dropwise adding the yttrium aqueous solution prepared in the step (2) into sodium bicarbonate with the concentration of 0.1mol/L under the stirring condition, uniformly mixing, then adding the graphene oxide-containing alcoholic solution prepared in the step (1), stirring for 3min at 500rpm of a magnetic stirrer, adding a sodium hydroxide solution to adjust the pH value of a reaction system to be more than 8.0, reacting for 1h under the water bath condition of 60 ℃, then adding a surface modifier, and aging for 12h to prepare a mixed solution;
(4) the particle diameter D is adjusted according to the mass ratio of 100:550LiNi of 5 μm0.7Co0.1Mn0.2O2Ternary materialMixing the materials with the mixed solution prepared in the step (3), uniformly stirring and mixing, filtering and drying to prepare powder with modified surface;
(5) and (4) carrying out heat treatment on the powder subjected to surface modification in the step (4) at 550 ℃ for 6 hours to obtain the nano yttrium oxide graphene modified nickel cobalt lithium manganate composite material.
Example 3
A preparation method of a yttrium oxide graphene modified nickel cobalt lithium manganate composite material for a lithium ion battery comprises the following steps:
(1) ultrasonically dispersing 0.1g of graphene oxide in 100mL of ethanol solvent for 30min to obtain an alcoholic solution containing the graphene oxide;
(2) dissolving yttrium nitrate in 100mL of water to prepare an yttrium water solution with the mass fraction of 5 wt%;
(3) dropwise adding the yttrium aqueous solution prepared in the step (2) into sodium bicarbonate with the concentration of 0.1mol/L under the stirring condition, uniformly mixing, then adding the graphene oxide-containing alcoholic solution prepared in the step (1), stirring for 3min at 500rpm of a magnetic stirrer, adding a sodium hydroxide solution to adjust the pH value of a reaction system to be more than 8.0, reacting for 1h under the water bath condition of 60 ℃, then adding a surface modifier, and aging for 12h to prepare a mixed solution;
(4) the particle diameter D is adjusted according to the mass ratio of 100:550LiNi of 3.5 μm0.7Co0.1Mn0.2O2Mixing the ternary material with the mixed solution prepared in the step (3), uniformly stirring and mixing, filtering and drying to prepare surface-modified powder;
(5) and (4) carrying out heat treatment on the powder subjected to surface modification in the step (4) at 550 ℃ for 6 hours to obtain the nano yttrium oxide graphene modified nickel cobalt lithium manganate composite material.
Example 4
This example differs from example 1 in that: yttrium chloride was used instead of yttrium nitrate and the other processes were the same as in example 1.
Example 5
This example differs from example 2 in that: yttrium chloride was used instead of yttrium nitrate and the other processes were the same as in example 2.
Example 6
This example differs from example 3 in that: yttrium chloride was used instead of yttrium nitrate and the other processes were the same as in example 3.
Comparative example 1
This comparative example is a commercially available LiNi0.7Mn0.1Co0.2O2。
Performance test
To examine the nano-yttria graphene-modified lithium nickel cobalt manganese oxide composite materials prepared in examples 1 to 6 and commercial LiNi purchased in comparative example 10.7Mn0.1Co0.2O2Performance of (1), commercial LiNi on the market, purchased from nano yttrium oxide graphene-modified nickel cobalt lithium manganate composite materials prepared in examples 1 to 6 and comparative example 1, respectively0.7Mn0.1Co0.2O2As a positive electrode material, a lithium metal sheet is a negative electrode material, a button cell is assembled, the determination is carried out at the normal temperature of 25 ℃ or 45 ℃, under the voltage of 2.8-4.35V or 2.8-4.4V and under the multiplying power of 1C, the cyclic discharge is carried out for 50 times, and the capacity retention rate is detected, and the result is shown in table 1;
the detection method specifically comprises the following steps: uniformly mixing a positive electrode material, conductive carbon powder and an organic binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, adding 0.05mL of NMP solvent, fully stirring to obtain viscous slurry, uniformly coating the viscous slurry on the surface of an aluminum foil, drying by blowing, placing in a vacuum drying oven at 120 ℃ for drying for 8 hours, and rolling to obtain a positive electrode plate; evaluating the electrochemical performance of the obtained ternary cathode material by using a 2016 type half cell; and (3) stamping the rolled battery pole piece into a wafer with the diameter of 12mm, accurately weighing the mass of the wafer, calculating the mass of the ternary positive electrode material in the pole piece according to the formula composition, wherein the diameter of the used diaphragm is 19mm, the diameter of the used negative electrode lithium piece is 15mm, and assembling the wafer into the testable button battery in a Germany Braun glove box.
Table 1 shows the results of the measurement of the properties of the products of examples 1 to 6 and comparative example 1
| Temperature, voltage | 0.2C first discharge capacitance Quantity (mAh/g) | 0.2C first discharge Efficiency (%) | 0.33C discharging capacity-limiting Quantity (mAh/g) | 1C discharge gram capacity （mAh/g） | 50 cycle capacity Retention (%) | |
| Comparison of Example 1 | （25℃、2.8- 4.35V） | 184.5 | 83.45 | 179.6 | 169.8 | 94.55 |
| Comparison of Example 1 | （25℃、2.8- 4.35V） | 187 | 84.2 | 181.6 | 172.1 | 93.2 |
| Comparison of Example 1 | （45℃、2.8- 4.35V） | 188 | 84.9 | 181.7 | 171.9 | 90.3 |
| Practice of Example 1 | （25℃、2.8- 4.35V） | 186.2 | 85.26 | 183.2 | 173.8 | 95.73 |
| Practice of Example 1 | （25℃、2.8- 4.4V） | 189.5 | 85.5 | 187.5 | 177.2 | 94.80 |
| Practice of Example 1 | （45℃、2.8- 4.35V） | 190.1 | 86.2 | 188.4 | 177.8 | 90.4 |
| Practice of Example 2 | （25℃、2.8- 4.35V） | 186.8 | 85.79 | 183.5 | 173.9 | 96.38 |
| Practice of Example 3 | （25℃、2.8- 4.35V） | 186.5 | 85.78 | 182.6 | 173.8 | 95.85 |
| Practice of Example 4 | （25℃、2.8- 4.35V） | 186.0 | 85.58 | 183.3 | 175.8 | 95.96 |
| Practice of Example 5 | （25℃、2.8- 4.35V） | 186.7 | 85.26 | 183.6 | 175.4 | 95.56 |
| Practice of Example 6 | （25℃、2.8- 4.35V） | 187.3 | 85.79 | 183.3 | 174.6 | 95.55 |
In conclusion, compared with the traditional method for directly coating the ternary cathode material by using the inert material, the method adopts an in-situ coating process and a high-temperature post-treatment process, and coats the nickel cobalt lithium manganate ternary cathode material core to form the surface modified layer;
when the prepared yttrium oxide graphene modified nickel cobalt lithium manganate composite material is used for a lithium ion battery, the positive electrode material is high in lithium ion and electron conductivity and good in electrochemical performance, so that the lithium ion battery has high specific capacity and long service life.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation method of a yttrium oxide graphene modified nickel cobalt lithium manganate composite material for a lithium ion battery is characterized by comprising the following steps:
(1) ultrasonically dispersing 0.05-0.5g of graphene oxide in 100mL of ethanol solvent for 10-90min to obtain an alcoholic solution containing the graphene oxide;
(2) dissolving soluble yttrium inorganic salt in 100mL of water to prepare yttrium water solution with the mass fraction of 1-10%;
(3) dropwise adding the yttrium aqueous solution prepared in the step (2) into a precipitator with the concentration of 0.1-0.5mol/L under the stirring condition, uniformly mixing, then adding the graphene oxide-containing alcoholic solution prepared in the step (1), stirring for 1-30min by a magnetic stirrer, adding a sodium hydroxide solution to adjust the pH value of a reaction system to be not less than 7.5, reacting for 0.5-2h under the water bath condition of 50-100 ℃, then adding a surface modifier, and aging for 10-48h to prepare a mixed solution;
(4) mixing the mixed solution prepared in the step (3) with a nickel cobalt lithium manganate ternary material, uniformly stirring and mixing, filtering, and drying to obtain surface modified powder;
(5) carrying out heat treatment on the powder subjected to surface modification and prepared in the step (4), wherein the heat treatment temperature is 300-800 ℃, and the heat treatment time is 1-10h, so as to prepare the nano yttrium oxide graphene modified nickel cobalt lithium manganate composite material;
the surface modifier in the step (3) comprises tetraethoxysilane or methyl orthosilicate;
the mass of the surface modifier in the step (3) is 0.01-0.5 wt% of the mass of the yttrium aqueous solution.
2. The preparation method of the yttrium oxide graphene modified nickel cobalt lithium manganate composite material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the soluble yttrium inorganic salt in the step (2) comprises yttrium-containing hydrochloride or yttrium-containing nitrate.
3. The preparation method of the yttrium oxide graphene modified nickel cobalt lithium manganate composite material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: and (3) the precipitating agent in the step (3) comprises one or more of bicarbonate, acetate, carbonate and oxalate.
4. The preparation method of the yttrium oxide graphene modified nickel cobalt lithium manganate composite material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the nickel cobalt lithium manganate ternary material in the step (4) is LiNixCoyMn(1-x-y)O2Wherein x is more than or equal to 0.6, y is more than 0 and less than or equal to 0.4, and 1-x-y is more than 0; the particle diameter D of the nickel cobalt lithium manganate ternary material50And 3.5 μm.
5. The preparation method of the yttrium oxide graphene modified nickel cobalt lithium manganate composite material for the lithium ion battery according to claim 4, wherein the preparation method comprises the following steps: the mass ratio of the nickel cobalt lithium manganate ternary material to the mixed solution in the step (4) is 100: 1-10.
6. The preparation method of the yttrium oxide graphene modified nickel cobalt lithium manganate composite material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the step of heat treatment in step (5) is carried out in an air or oxygen atmosphere.
7. The yttrium oxide graphene-modified nickel cobalt lithium manganate composite material prepared by the preparation method of the yttrium oxide graphene-modified nickel cobalt lithium manganate composite material for lithium ion batteries according to any one of claims 1 to 6.
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