CN107946576B - High-rate graphite negative electrode material, preparation method thereof and lithium ion battery - Google Patents
High-rate graphite negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention relates to a high-rate graphite negative electrode material, a preparation method thereof and a lithium ion battery. The high-rate graphite cathode material comprises a graphite inner core and a hard carbon material layer coated on the surface of the graphite inner core, wherein the hard carbon material layer is doped with lithium nitride. According to the high-rate graphite cathode material provided by the invention, the hard carbon material is doped and modified by using the lithium nitride, so that on one hand, the structural relation between the core and the coating layer can be established by using the lithium affinity of the core and the hard carbon material, and the affinity and the structural stability of the core and the coating layer are improved; on the other hand, the lithium nitride doping can form lattice defects in the carbon layer, improve the mobility of electrons, increase lithium storage binding points, increase the interlayer spacing of the carbon-based material and improve the migration rate of lithium ions, and the graphite cathode material has the characteristics of good structural stability, large interlayer spacing, more lithium storage binding points and high lithium ion and electron transmission rate, and can greatly improve the quick charging capacity of the lithium ion battery.
Description
Technical Field
The invention belongs to the field of preparation of graphite cathode materials, and particularly relates to a high-rate graphite cathode material, a preparation method thereof and a lithium ion battery.
Background
With the rapid development of electric vehicles, lithium ion batteries with high energy density and high charging and discharging speed are increasingly popular in the market. The negative electrode material is an important factor for restricting the improvement of the quick charge capacity of the lithium ion battery. The current marketable negative electrode material mainly takes a graphite material as a main material, although the graphite material has certain advantages in the aspects of structural stability, structural order, cost, cycle performance and the like, the small interlayer spacing of the material determines the rate charge and discharge capacity deviation of the graphite negative electrode, and the risk of lithium precipitation exists during rapid charging. Modification of graphite materials is one of the methods for improving the quick charging capacity of the negative electrode materials.
The patent with application publication number CN102306796A discloses a composite graphite negative electrode material, which comprises a natural graphite core and a coating layer coated on the surface of the natural graphite core, wherein the coating layer is hard carbon formed by carbonizing phenolic resin. The composite graphite cathode material is prepared by coating and modifying natural graphite by using hard carbon, so that the charge and discharge performance of the lithium ion battery can be improved to a certain extent by utilizing the characteristics of large spacing and disordered structure of hard carbon material layers, but the quick charge capacity is still insufficient.
Disclosure of Invention
The invention aims to provide a high-rate graphite negative electrode material, so that the problem of poor quick charging capability of the conventional graphite negative electrode material is solved.
The second purpose of the invention is to provide a preparation method of the high-rate graphite negative electrode material.
The third purpose of the invention is to provide a lithium ion battery using the high-rate graphite negative electrode material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the high-rate graphite negative electrode material comprises a graphite core and a hard carbon material layer coated on the surface of the graphite core, wherein the hard carbon material layer is doped with lithium nitride.
According to the high-rate graphite cathode material provided by the invention, the hard carbon material is doped and modified by using the lithium nitride, so that on one hand, the structural relation between the core and the coating layer can be established by using the lithium affinity of the core and the hard carbon material, and the affinity and the structural stability of the core and the coating layer are improved; on the other hand, the lithium nitride doping can form lattice defects in the carbon layer, improve the mobility of electrons, increase lithium storage binding points, increase the interlayer spacing of carbon materials and improve the migration rate of lithium ions; meanwhile, the lithium nitride material is a lithium fast ion conductor and has certain electron conductivity, so that the migration rate of electrons and the capacity exertion of the material are improved; under the combined action of the above factors, the graphite cathode material has the characteristics of good structural stability, large interlayer spacing, multiple lithium storage binding points and high lithium ion and electron transmission rate, and further can greatly improve the quick charge capacity of the lithium ion battery.
Preferably, the hard carbon material layer is further doped with N, B, S, Cl or F. By doping elements such as N, B, S, Cl and F, the electronic conductivity of the negative electrode material can be further improved, and the rate charge-discharge performance and the capacity exertion of the negative electrode material can be further improved.
The thickness of the hard carbon material layer is 100-500 nm.
The technical scheme adopted by the high-rate graphite negative electrode material is as follows:
a preparation method of a high-rate graphite negative electrode material comprises the following steps:
1) adding a hard carbon precursor, passivated lithium powder and graphite into a non-aqueous solvent, uniformly mixing, and performing spray drying to prepare precursor particles;
2) and reacting the precursor particles with nitrogen to prepare a lithium nitride doped precursor, and then carbonizing and sintering the lithium nitride doped precursor to obtain the lithium nitride doped lithium ion material.
Step 1) is a precursor particle preparation step, in which a hard carbon precursor and passivated lithium powder are coated on a graphite core through liquid phase mixing and spray drying.
In order to further obtain a better liquid phase mixing effect, preferably, the hard carbon precursor is mixed with a non-aqueous solvent, and then the passivated lithium powder is added and uniformly mixed to obtain a coating solution; then adding graphite into the coating liquid, uniformly mixing, and preparing precursor particles by utilizing spray drying.
The non-aqueous solvent is an alcohol solvent. Preferably, the alcohol solvent is ethanol. The hard carbon precursor can be conveniently dissolved in ethanol. The non-aqueous solvent used in this step can be any solvent that can avoid reaction with the passivated lithium powder, and other organic solvents known in the art, such as diethyl ether, dichloromethane, etc., can also be used.
The hard carbon precursor is a precursor polymer for preparing the hard carbon material, which can be a conventional organic polymer for preparing the hard carbon material, and preferably, the hard carbon precursor is one or more of phenolic resin, epoxy resin, furfural resin and acrylic resin. The passivated lithium powder is a conventional commercial product. Preferably, the graphite is natural graphite.
The mass ratio of the hard carbon precursor to the passivated lithium powder to the graphite is (1-10): (0.1-1): 100. if the hard carbon precursor and the passivated lithium powder exceed or fall below the ranges, the coating effect is poor or the subsequent doping effect is influenced, and the mass ratio of the hard carbon precursor to the passivated lithium powder is controlled within the ranges, so that precursor particles with uniform particle size distribution and good coating effect can be obtained.
And step 2) doping lithium nitride by reacting lithium in the precursor particles with nitrogen, and preparing hard carbon by carbonization and sintering.
In the step 2), the reaction is to react the precursor particles with nitrogen by utilizing the electric spark deposition. The step is to utilize an electric spark deposition technology to discharge between an electrode and a metal matrix to generate electric sparks so as to initiate precursor particles on the metal matrix to react with nitrogen. Preferably, in the electric spark deposition process, the power supply for generating electric sparks is 600-800W, the voltage is 80-120V, and the frequency is 500-1000 Hz.
The preparation method of the lithium nitride doped precursor by the electric spark deposition technology has the advantages of high synthesis rate, controllable process, high consistency, suitability for industrial production and the like.
In the step 2), the lithium nitride doping precursor and the doping agent containing N, B, S, Cl or F element are mixed, and then the carbonization sintering is carried out. The doping agent containing N, B, S, Cl or F is pyrrole, pyridine, thiophene, aniline、N2H4Silicon fluoride, borazene or carbon tetrachloride.
Preferably, the mixing is ethanol solution mixing of the lithium nitride doping precursor and the dopant. More preferably, the mass concentration of the dopant in the ethanol solution of the dopant is 1 to 10%.
The carbonization sintering is carried out in an ammonia atmosphere. Preferably, the carbonization sintering is carried out for 2-12 h at the temperature of 600-800 ℃. And sintering in ammonia atmosphere to react ammonia with hydroxyl carboxyl on the surface of the carbon-based material and dope nitrogen element on the surface of carbon. The sintering conditions are adopted for sintering, the sintering temperature is low, the process is simple, and the quality stability of the obtained product is good.
On the basis of the high-rate graphite negative electrode material, the corresponding negative electrode plate and the lithium ion battery can be prepared by utilizing the known technology of the technicians in the field. For example, the negative electrode material, the conductive agent, the binder and the solvent are mixed to prepare negative electrode material slurry, then the negative electrode material slurry is coated on copper foil, and the negative electrode pole piece is prepared through drying and mould pressing. Then taking ternary material as a positive electrode and LiPF6The solution is used as electrolyte, PE, PP or composite membrane is used as diaphragm, and lithium ion battery with various forms is assembled according to the prior art.
The lithium ion battery adopting the high-rate graphite cathode material has high first discharge capacity and first efficiency, and the cycle performance, rate performance and low-temperature performance are improved comprehensively.
Drawings
Fig. 1 is an SEM image of the high-magnification graphite negative electrode material of example 1;
fig. 2 is a graph of the rate charge of the lithium ion battery of example 1.
Detailed Description
The following examples are provided to further illustrate the practice of the invention. In the following examples, the phenolic resin has a softening point of 64-68 ℃, a conductivity of not more than 2 μ s/cm, a hydroxyl equivalent of 103-107g/eq, a model of PF-8606, and is available from the Jensen Hawas chemical Co., Ltd. The epoxy resin has an epoxy equivalent of 185-197g/eq, hydrolysis chlorine of less than or equal to 300ppm, a melting point of 138-146 ℃, chloride ion of less than or equal to 300ppm, a model of SQE-101, and is purchased from the Jinan Shengquan Haiwos chemical Co., Ltd. The softening point of the furfural resin is 105-125 ℃, the hydroxyl equivalent is 70-120g/eq, the conductivity is less than or equal to 1 mu s/cm, the model is INT-105, and the furfural resin is purchased from Jinan Shengquan Haiwos chemical Co. The type of the passivated lithium powder is Li-1, and is purchased from Tianjin lithium industry Co.
Example 1
The high-rate graphite cathode material comprises a graphite core and a hard carbon material layer doped on the surface of the graphite core, wherein the hard carbon material layer is doped with lithium nitride, and the thickness of the hard carbon material layer is 100 nm.
The preparation method of the high-rate graphite negative electrode material of the embodiment adopts the following steps:
1) adding 5g of phenolic resin into 500mL of ethanol, uniformly dispersing, adding 0.5g of passivated lithium powder, and uniformly dispersing again to obtain a coating solution; then adding 100g of natural graphite into the coating liquid, uniformly mixing, and preparing precursor particles through spray drying;
2) under the nitrogen atmosphere, adopting electric spark deposition to enable precursor particles to react with nitrogen, and preparing a lithium nitride doped precursor; the power of a power supply for generating electric sparks is 750W, the voltage is 100V, and the output power is 800 Hz;
3) soaking the lithium nitride doped precursor in a pyrrole solution (ethanol is used as a solvent) with the mass concentration of 5% for 3h, filtering and drying, then transferring filter residues into a tubular furnace, heating to 700 ℃ in an ammonia atmosphere, keeping the temperature for 6h, stopping introducing ammonia, and then introducing argon to naturally cool to room temperature to obtain the lithium nitride doped precursor.
In the lithium ion battery of this example, 9g of the negative electrode material of this example, 0.5g of the conductive agent SP, 0.5g of the 0.5gLA132 binder, and 220mL of water were mixed to prepare a negative electrode material slurry; coating the slurry of the negative electrode material on a copper foil, drying and rolling to prepare a negative electrode; then using ternary material (LiNi)1/3Co1/3Mn1/3O2) As a positive electrode, 1.3mol/L LiPF6The solution (the solvent is formed by mixing EC and DEC according to the volume ratio of 1: 1) is used as electrolyte, celegard2400 is used as a diaphragm, and the 10Ah soft package lithium ion battery is assembled according to the prior artAnd (4) a pool.
Example 2
The high-rate graphite negative electrode material comprises a graphite core and a hard carbon material layer doped on the surface of the graphite core, wherein the hard carbon material layer is doped with lithium nitride and an element S, and the thickness of the hard carbon material layer is 300 nm.
The preparation method of the high-rate graphite negative electrode material of the embodiment adopts the following steps:
1) adding 1g of epoxy resin into 500mL of ethanol, uniformly dispersing, adding 0.1g of passivated lithium powder, and uniformly dispersing again to obtain a coating solution; then adding 100g of natural graphite into the coating liquid, uniformly mixing, and preparing precursor particles through spray drying;
2) under the nitrogen atmosphere, adopting electric spark deposition to enable precursor particles to react with nitrogen, and preparing a lithium nitride doped precursor; the power of a power supply for generating electric sparks is 600W, the voltage is 80V, and the output power is 500 Hz;
3) soaking the lithium nitride doped precursor in a thiophene solution (ethanol is used as a solvent) with the mass concentration of 1% for 1h, filtering and drying, then transferring filter residues into a tubular furnace, heating to 600 ℃ in an ammonia atmosphere, keeping the temperature for 12h, stopping introducing ammonia, and then introducing argon to naturally cool to room temperature to obtain the lithium nitride doped precursor.
The lithium ion battery of this example adopts the negative electrode material of this example, and the 10Ah soft package lithium ion battery is prepared by referring to the method of example 1.
Example 3
The high-rate graphite negative electrode material comprises a graphite core and a hard carbon material layer doped on the surface of the graphite core, wherein the hard carbon material layer is doped with lithium nitride, and the thickness of the hard carbon material layer is 500 nm.
The preparation method of the high-rate graphite negative electrode material of the embodiment adopts the following steps:
1) adding 10g of furfural resin into 500mL of ethanol, adding 1g of passivated lithium powder after uniform dispersion, and dispersing uniformly again to obtain a coating solution; then adding 100g of natural graphite into the coating liquid, uniformly mixing, and preparing precursor particles through spray drying;
2) under the nitrogen atmosphere, adopting electric spark deposition to enable precursor particles to react with nitrogen, and preparing a lithium nitride doped precursor; the power of a power supply for generating electric sparks is 800W, the voltage is 120V, and the output power is 1000 Hz;
3) soaking the lithium nitride doped precursor in an aniline solution (the solvent is ethanol) with the mass concentration of 10% for 12h, filtering, drying, transferring filter residue into a tubular furnace, heating to 800 ℃ in an ammonia atmosphere, keeping the temperature for 2h, stopping introducing ammonia, introducing argon, and naturally cooling to room temperature to obtain the lithium nitride doped precursor.
The lithium ion battery of this example adopts the negative electrode material of this example, and the 10Ah soft package lithium ion battery is prepared by referring to the method of example 1.
In other embodiments of the high-rate graphite negative electrode material of the present invention, the hard carbon precursor may be equivalently replaced with acrylic resin according to the method of embodiment 3, and equivalently replaced with borazine, hydrazine, carbon tetrachloride, silicon fluoride, or pyridine as dopants, so as to obtain a negative electrode material with equivalent performance.
Comparative example 1
The graphite negative electrode material of comparative example 1 was prepared by the following steps:
1) adding 5g of phenolic resin into 500mL of ethanol, uniformly dispersing, adding 1g of lithium nitride, and uniformly mixing to obtain a coating solution; then adding 100g of natural graphite into the coating liquid, and preparing a lithium nitride-doped precursor through spray drying;
2) and transferring the lithium nitride doped precursor into a tubular furnace, heating to 700 ℃ in an ammonia atmosphere, keeping the temperature for 6h, stopping introducing ammonia, introducing argon, and naturally cooling to room temperature to obtain the lithium nitride doped precursor.
A 10Ah soft pack lithium ion battery was prepared by the method of reference example 1 using the graphite anode material of comparative example 1.
Comparative example 2
The graphite negative electrode material of comparative example 2 was prepared by the following steps:
1) adding 5g of phenolic resin into 500mL of ethanol, and uniformly dispersing to obtain a coating solution; then adding natural graphite into the coating liquid, and preparing precursor particles through spray drying;
2) soaking the precursor particles in 5 wt% pyrrole solution (ethanol as solvent), filtering, drying, transferring the filter residue to a tubular furnace, heating to 700 deg.C under ammonia atmosphere, keeping the temperature for 6h, stopping introducing ammonia, introducing argon, and naturally cooling to room temperature.
The graphite anode material of comparative example 2 was used to prepare a 10Ah soft pack lithium ion battery by the method of reference example 1.
Test example 1
The test example examined the appearance of the high-rate graphite negative electrode material of example 1, and as a result, as shown in fig. 1, it was found that the high-rate graphite negative electrode material of example 1 had a spheroidal appearance, a dense and uniform coating layer, and a particle diameter of 8 to 15 μm.
Test example 2
In the test example, the specific surface area, tap density and interlayer spacing of the negative electrode materials of the examples and the comparative examples are determined according to the method specified in GB/T243358-2009 lithium ion battery graphite negative electrode material, wherein the interlayer spacing is the detection result of the hard carbon material on the surface of the material.
Respectively weighing 9g of the negative electrode material, 0.5g of conductive agent SP and 0.5g of LA132 binder of each example and comparative example, adding the materials into 220mL of deionized water, uniformly stirring, coating the mixture on a copper foil to manufacture a membrane, and then taking a lithium sheet as a negative electrode, a celegard2400 as a membrane and 1mol/L LiPF6The solution (solvent is formed by mixing EC and DMC in a volume ratio of 1: 1) is used as electrolyte, the button cell is assembled in a glove box with oxygen and water contents lower than 0.1ppm, then the first discharge capacity and the first efficiency of each button cell are tested on a blue electricity tester, the button cell is charged and discharged at a rate of 0.1C during detection, the button cell is stopped after circulating for 3 weeks in a voltage range of 0.05V-2.0V, and the detection results are shown in Table 1.
TABLE 1 comparison of the performances of the negative electrode materials and button cells of the examples and comparative examples
As can be seen from the results in table 1, the negative electrode materials of the examples have superior first efficiency and gram-capacity to the comparative examples, because the lattice defects generated by doping of the lithium nitride can bring more lithium binding sites, increase the interlayer spacing of the hard carbon material, and the lithium nitride material itself can promote the transport of lithium ions, thereby improving the gram-capacity and lithium storage performance of the negative electrode materials. According to the data of the specific surface area, the tap density, the interlayer spacing and the like of the cathode material, the cathode material prepared by the method has larger specific surface area and tap density, the interlayer spacing is further increased, and the factors are favorable for further improving the gram capacity of the cathode material.
Test example 3
The test examples test the cycle performance, rate performance and low-temperature discharge performance of the pouch ion batteries of the examples and the comparative examples, wherein in the rate performance test, the charging currents are 1C, 5C, 10C, 20C, 25C and 30C, the discharging currents are 1C, the voltage range is 3.0-4.1V, and the constant current ratio is constant current charging capacity/(constant current charging capacity + constant voltage charging capacity). During the cycle performance test, the charge-discharge current is 3C/3C, the voltage range is 3.0-4.1V, and the cycle times are 500 times. When the low-temperature discharge performance is detected, the charging current is 1C, the discharging current is 1C, and the discharging test temperatures are respectively 25 ℃, 0 ℃, 20 ℃ and 30 ℃. The results of the measurements are shown in tables 2 and 3.
Table 2 comparison of rate charging performance of soft-packed lithium ion batteries of each example and comparative example
The detection data in table 2 show that the soft-package lithium ion battery prepared in the embodiment has a higher constant current ratio and shows better quick charging performance, and therefore, the method provided by the invention can be used for modifying the hard carbon material, so that the high-rate charging performance of the graphite cathode material can be greatly optimized, and the requirement of an electric vehicle on the quick charging performance can be met.
Fig. 2 is a battery rate charging curve of the soft package lithium ion battery of example 1 at 1C, 5C, 10C, 20C, 25C, and 30C, and it can be seen from fig. 2 that the battery of example has a higher constant current ratio, i.e., a higher quick-charging capability.
Table 3 low temperature discharge performance and cycle performance of soft pack lithium ion batteries of each example and comparative example
The results in table 3 show that the soft-package lithium ion battery of the embodiment is significantly better than the comparative example in terms of low-temperature discharge and capacity retention rate thereof, and the reason is that the doping modification of the hard carbon material by using the method of the present invention can improve the interlayer spacing of the hard carbon material, increase the transmission rate of lithium ions of the negative electrode material under a low-temperature condition, and further facilitate the improvement of the low-temperature discharge retention rate and the high-rate cycle performance of the negative electrode material.
The results in tables 2 and 3 show that the lithium ion battery provided by the invention has the advantages of fast charge performance, low-temperature discharge performance and high-rate cycle performance, and the lithium nitride is doped in the hard carbon material and modified by the impurity elements, so that the effects of improving the transmission rate and the electronic conduction rate of lithium ions and increasing the lithium storage binding points can be achieved, the lithium ions can be promoted to be rapidly inserted and removed from multiple directions in the charge and discharge process, the fast charge performance of the negative electrode material is improved, the low-temperature performance and the cycle performance are improved, the lithium ion battery is more suitable for the adaptability of the current electric automobile to the fast charge and discharge of the lithium ion battery and the low-temperature environment, and the cycle life of the lithium ion battery is prolonged.
Claims (10)
1. The high-rate graphite cathode material is characterized by comprising a graphite core and a hard carbon material layer coated on the surface of the graphite core, wherein the hard carbon material layer is doped with lithium nitride.
2. The high-rate graphite anode material according to claim 1, wherein the hard carbon material layer is further doped with N, B, S, Cl or F.
3. The high-rate graphite anode material as claimed in claim 1 or 2, wherein the thickness of the hard carbon material layer is 100-500 nm.
4. The preparation method of the high-rate graphite anode material as claimed in claim 1, characterized by comprising the following steps:
1) adding a hard carbon precursor, passivated lithium powder and graphite into a non-aqueous solvent, uniformly mixing, and performing spray drying to prepare precursor particles;
2) and reacting the precursor particles with nitrogen to prepare a lithium nitride doped precursor, and then carbonizing and sintering the lithium nitride doped precursor to obtain the lithium nitride doped lithium ion material.
5. The method for preparing the high-rate graphite anode material according to claim 4, wherein in the step 1), the hard carbon precursor is one or more of phenolic resin, epoxy resin, furfural resin and acrylic resin.
6. The preparation method of the high-rate graphite negative electrode material as claimed in claim 4 or 5, wherein in the step 1), the mass ratio of the hard carbon precursor to the passivated lithium powder to the graphite is (1-10): (0.1-1): 100.
7. the method for preparing the high-rate graphite negative electrode material according to claim 4, wherein in the step 2), the lithium nitride doping precursor and the doping agent containing N, B, S, Cl or F are mixed, and then the carbonization sintering is performed.
8. The method for preparing the high-rate graphite anode material according to claim 4 or 7, wherein in the step 2), the reaction is carried out by reacting the precursor particles with nitrogen by using spark deposition.
9. The preparation method of the high-rate graphite cathode material as claimed in claim 8, wherein in the step 2), in the electric spark deposition process, the power supply power for generating electric sparks is 600-800W, the voltage is 80-120V, and the frequency is 500-1000 Hz.
10. A lithium ion battery using the high-rate graphite negative electrode material of claim 1.
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| CN110247054B (en) * | 2019-06-28 | 2020-10-30 | 蜂巢能源科技有限公司 | Graphite composite negative electrode material, preparation method thereof and battery |
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| CN114709398B (en) * | 2022-04-17 | 2022-12-06 | 晖阳(贵州)新能源材料有限公司 | Sulfur-containing fast ion conductor coated graphite composite material and preparation method thereof |
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| CN1877888A (en) * | 2006-05-19 | 2006-12-13 | 清华大学 | Hard carbon-metal lithium nitride composite cathode materials and method for preparing same |
| CN105098185A (en) * | 2014-04-29 | 2015-11-25 | 华为技术有限公司 | Composite cathode material, preparation method thereof, lithium ion secondary battery negative plate and lithium ion secondary battery |
| CN104269555A (en) * | 2014-10-08 | 2015-01-07 | 深圳市贝特瑞新能源材料股份有限公司 | Soft carbon anode material for lithium-ion power and energy storage battery as well as preparation method and application of soft carbon anode material |
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