CN114853004A - Negative electrode material and preparation method and application thereof - Google Patents
Negative electrode material and preparation method and application thereof Download PDFInfo
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- CN114853004A CN114853004A CN202210441218.5A CN202210441218A CN114853004A CN 114853004 A CN114853004 A CN 114853004A CN 202210441218 A CN202210441218 A CN 202210441218A CN 114853004 A CN114853004 A CN 114853004A
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Abstract
The invention provides a negative electrode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing the template material and graphite, and heating for reaction to obtain a template material-graphite intercalation compound; (2) transferring the template material-graphite intercalation compound obtained in the step (1) into a polypropylene container, performing microwave treatment to obtain a metal oxide-graphite intercalation compound, and reducing the metal oxide-graphite intercalation compound to obtain a metal-graphite intercalation compound; (3) the metal-graphite intercalation compound obtained in the step (2) is mixed with an acid solution, and the anode material is obtained after stirring reaction.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a negative electrode material, and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) have the advantages of high energy density, high power density, long cycle life, low price, and the like, and are considered to be the best choice for next-generation large-scale energy storage systems or Electric Vehicles (EVs) to surpass non-renewable energy sources. At present, the methodLithium ion batteries have been widely used in portable electronic products, and their application range is still expanding rapidly, and the recent huge demand for new energy automobiles has more stimulated the rapid growth of the lithium ion battery market. Since the advent of lithium ion batteries, a variety of different positive electrode materials have successfully entered the market, including LiCoO 2 (LCO)、LiFePO 4 (LFP)、LiMn 2 O 4 (LMO)、LiNiO 2 (LNO)、LiNi 1-y-z CoyMn z O 2 (NMC) and LiNi 1-y-z CoyAl z O 2 (NCA), but graphite is still the most practical anode material, accounting for 98% of the market share, while Li 4 Ti 5 O 12 The (LTO) negative electrode has only a 2% market share due to the relatively low cost of graphite, abundant reserves, good electrical conductivity, long cycle life, low delithiation/lithiation potential and high energy density. Some of the anode materials currently under investigation have higher rate capability, such as silicon (4200mAh/g), tin (993mAh/g) and its alloys, hydrides, oxides and phosphides, however, these emerging anode materials suffer from large volume expansion during lithium ion insertion/extraction, resulting in capacity loss during cycling.
The graphite consists of a series of parallel sp 2 Hybrid graphene layers are constructed in such a way that in each layer, a carbon atom is covalently linked to three other carbons to form a honeycomb lattice with a bond length of 0.142nm, and hybrid electrons migrate freely in the layer and interact with another delocalized electron in an adjacent layer by weak van der waals forces, with a layer-to-layer distance of 0.335 nm. The layered structure allows lithium ions to be intercalated and deintercalated between layers and forms a lithium-graphite intercalation compound. The intercalation process is a reversible reaction in which a lithium-carbon alloy (Li) is formed x C n ). During charging, lithium ions can form LiC with highly crystalline graphite 6 The lithium-graphite intercalation compound in the form which is theoretically the maximum for lithium ion intercalation has a theoretical capacity of 372mAh/g and the average delithiation/lithiation potential of the process is low, only 0.2V vs Li/Li + This results in a relatively small voltage lag between charging and discharging potentials and a higher energy efficiency.Since the discovery of this reversible intercalation behavior of lithium ions in graphite, lithium ion intercalated graphite has replaced lithium metal as the negative electrode of lithium ion batteries.
CN107749472A discloses a graphite composite negative electrode material, which has a core-shell structure, and includes an inner core part and an outer shell part wrapped in the inner core part, wherein the inner core part is a germanium oxide-graphite composite material, the outer shell part is an inorganic lithium composite, and the outer shell part of the graphite composite negative electrode material has a pore structure. The metal composite material or the metal coating can be used for modifying the graphite electrode, promoting the formation of an SEI film, reducing the resistance of the SEI film and leading to higher reaction kinetics in the lithium removal/lithiation process. The method has high operation difficulty, and the thickness and quality of the introduced modification layer need to be accurately controlled. Another approach is to inject small amounts of electrolyte additives that kinetically favor the formation of the SEI layer, thereby increasing the initial coulombic efficiency. For example, fluoroethylene carbonate (FEC), ethylene sulfite, propylene sulfite, and the like, but they are less stable.
CN114203979A discloses a preparation method of a graphite negative electrode material, which comprises the following steps: s1, mixing the catalyst and the binder, heating and preserving heat under the inert atmosphere or vacuum condition, cooling to room temperature, and crushing; s2, mixing the substance obtained in the step S1 with crystalline flake graphite, and carrying out spheroidization to obtain spherical graphite particles; s3, mixing the obtained spherical graphite particles with a binder, simultaneously rotating and heating the obtained mixture, cooling and discharging; and S4, carrying out high-temperature graphitization, demagnetization and screening to obtain the graphite cathode material.
The graphite cathode material in the scheme has the problems of poor rate capability or low charge and discharge efficiency, so that the development of the graphite cathode material with good rate capability and high charge and discharge efficiency is necessary.
Disclosure of Invention
The invention aims to provide a negative electrode material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an anode material, comprising the steps of:
(1) mixing the template material and graphite, and heating for reaction to obtain a template material-graphite intercalation compound;
(2) transferring the template material-graphite intercalation compound obtained in the step (1) into a container, performing microwave treatment to obtain a metal oxide-graphite intercalation compound, and reducing the metal oxide-graphite intercalation compound to obtain a metal-graphite intercalation compound;
(3) and (3) mixing the metal-graphite intercalation compound (metal-GIC) obtained in the step (2) with an acid solution, and stirring for reaction to obtain the negative electrode material.
The invention uses the hard template to prepare the porous graphite material, successfully replaces the traditional commercial graphite material to be used as the lithium ion battery cathode material, the porous structure is favorable for the electrolyte permeation, thereby leading to the increase of the contact area of the electrode and the electrolyte, the small particle size provides a shorter diffusion path for lithium ions in the de-intercalation/intercalation process, and the lithium ion transmission rate is improved.
Preferably, the template material of step (1) comprises FeCl 3 、FeCl 2 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 、CuCl 2 Or Mn (NO) 3 ) 2 Any one or a combination of at least two of them.
Preferably, the mass ratio of the template material to the graphite is (1-10): 1, such as: 1:1, 3:1, 5:1, 8:1, or 10:1, etc.
Preferably, the mixed atmosphere of step (1) is an inert atmosphere.
Preferably, the means for heating the reaction comprises an ampoule.
Preferably, before the heating reaction, vacuumizing for 25-40 min, for example: 25min, 30min, 32min, 35min or 40min and the like.
Preferably, the heating rate of the heating reaction is 4-6 ℃/min, for example: 4 ℃/min, 4.5 ℃/min, 5 ℃/min, 5.5 ℃/min, 6 ℃/min, or the like.
Preferably, the temperature of the heating reaction is 350-450 ℃, for example: 350 ℃, 380 ℃, 400 ℃, 420 ℃ or 450 ℃ and the like.
Preferably, the heating reaction time is 20-30 h, for example: 20h, 22h, 25h, 28h or 30h and the like.
Preferably, the heating reaction is followed by cooling, washing and drying.
Preferably, the washing detergent comprises ethanol.
Preferably, the container in step (2) comprises any one of a polypropylene container, a ceramic crucible or a glass container or a combination of at least two of the two.
Preferably, the microwave treatment device in step (2) comprises a microwave oven.
Preferably, the power of the microwave treatment is 600-800W, for example: 600W, 650W, 700W, 750W, 800W, etc.
Preferably, the microwave treatment time is 25-35 s, for example: 25s, 28s, 30s, 32s, or 35s, etc.
In the case of iron salts, FeCl 3 To Fe 2 O 3 Usually it is first necessary to convert the Fe (OH) under alkaline conditions 3 Then pyrolyzed to Fe 2 O 3 . The microwave method does not need to additionally add strong alkali such as NaOH and the like, and can utilize O in the air 2 Direct reaction to produce Fe 2 CO 3 。
Preferably, the atmosphere of the reduction in step (2) is an inert atmosphere.
Preferably, the inert atmosphere comprises nitrogen.
Preferably, the temperature of the reduction is 900-1100 ℃, for example: 900 deg.C, 950 deg.C, 1000 deg.C, 1050 deg.C or 1100 deg.C, etc.
Preferably, the reduction time is 0.5-1.5 h, such as: 0.5h, 0.8h, 1h, 1.2h or 1.5h and the like.
Preferably, the reduction is followed by a cooling treatment.
Preferably, the acid solution of step (3) comprises dilute hydrochloric acid.
Preferably, the mass ratio of the hydrogen chloride to the water in the dilute hydrochloric acid is (0.5-1.5) to 10, such as: 0.5:10, 0.8:10, 1:10, 1.2:10, or 1.5:10, etc.
Preferably, the temperature of the stirring reaction in the step (3) is 90-110 ℃, for example: 90 ℃, 95 ℃, 100 ℃, 105 ℃ or 110 ℃, etc.
Preferably, the stirring reaction time is 0.5-1.5 h, such as: 0.5h, 0.8h, 1h, 1.2h or 1.5h and the like.
Preferably, the stirring reaction is followed by sonication and filtration.
Preferably, the time of the ultrasonic treatment is 5-15 min, for example: 5min, 8min, 10min, 12min or 15min and the like.
Preferably, the step (3) is repeated for 2 to 3 times, for example: 2 times or 3 times.
Preferably, filtration is followed by vacuum drying.
Preferably, the temperature of the vacuum drying is 50-70 ℃, for example: 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃ and the like.
Preferably, the vacuum drying time is 10-15 h, for example: 10h, 11h, 12h, 13h, 14h or 15h, etc.
In a second aspect, the present invention provides a negative electrode material obtainable by a method as claimed in the first aspect.
In a third aspect, the invention provides a negative electrode plate, which comprises the negative electrode material according to the second aspect.
In a fourth aspect, the invention provides a lithium ion battery, which comprises the negative electrode plate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the porous structure is introduced into the graphite material with abundant reserves, so that the capacity of lithium ions is effectively increased, the first cycle irreversible capacity is reduced, the preparation process of the porous graphite material is simple, the reaction conditions are mild, the variety of the template material is wide, and the porous graphite material is cheap and easy to obtain.
(2) The first discharge gram capacity of the battery prepared from the negative electrode material can reach more than 363.4mAh/g, the second discharge gram capacity can reach more than 239.2mAh/g, the capacity retention rate can reach more than 65.8 percent, and the first discharge gram capacity of the battery can reach 392mAh/g, the second discharge gram capacity can reach 313.8mAh/g and the capacity retention rate can reach 65.8 percent by adjusting the material proportion and the reaction conditions in the preparation process.
Drawings
FIG. 1 is FeCl as described in example 1 3 -GIC、Fe 2 O 3 -X-ray diffraction (XRD) patterns of GIC, Fe-GIC and the negative electrode material.
FIG. 2 is FeCl after microwave treatment for 20s in example 1 3 SEM picture of GIC.
FIG. 3 is FeCl after microwave treatment for 20s in example 1 3 SEM magnification of GIC.
FIG. 4 is Fe as described in example 1 2 O 3 SEM picture of GIC.
FIG. 5 is Fe as described in example 1 2 O 3 SEM magnification of GIC.
FIG. 6 is an SEM picture of the Fe-GIC described in example 1.
FIG. 7 is an SEM micrograph of Fe-GIC as described in example 1.
Fig. 8 is an SEM image of the anode material according to example 1.
Fig. 9 is a plot of specific capacity versus cycle number for the anode material described in example 1.
Fig. 10 is a plot of specific capacity versus cycle number for the negative electrode material described in comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an anode material, which is prepared by the following method:
(1) FeCl is added 3 (0.48g) and graphite (0.08g) were mixed thoroughly under an argon atmosphere, the mixture was transferred to an ampoule and evacuated for 30 min. Then, the ampoule is sealed and heated to 400 ℃ in air at a heating rate of 5 ℃/min, the temperature is maintained for 24h, after cooling, the powder is washed with ethanol to remove excess FeCl 3 And dried at 60 ℃ to obtain FeCl 3 -GIC；
(2) FeCl to be synthesized 3 -GIC was transferred to a polypropylene container and irradiated in a microwave oven at 700W for 30s to obtain Fe 2 O 3 -GIC of said Fe 2 O 3 -reducing GIC at 1000 ℃ for 1h in a nitrogen atmosphere, and cooling to obtain Fe-GIC;
(3) transfer of Fe-GIC to Dilute hydrochloric acid (HCl/H) 2 O ═ 1:10) solution, the mixture was stirred and heated at 100 ℃ for 1 h. Then, it was sonicated for 10min and filtered. And repeating the steps twice, and performing vacuum drying at 60 ℃ for 12h to obtain the cathode material.
The FeCl 3 -GIC、Fe 2 O 3 X-ray diffraction (XRD) patterns of the-GIC, the Fe-GIC and the negative electrode material are shown in FIG. 1. As can be seen from FIG. 1, FeCl was present after the microwave treatment 3 The characteristic peak of GIC disappeared, but since the peak of graphite was very strong, Fe 2 O 3 The diffraction peaks of (A) were not significant, and the results ascribed to Fe were observed at 35.6 °, 54 °, 62.4 ° and 77.7 ° 2 O 3 The diffraction peak of (1). In N 2 After reduction under the conditions, diffraction peaks ascribed to Fe were observed at 44.7 ℃ and 65 ℃, indicating that Fe 2 O 3 Successfully reduced to Fe. After acid treatment, the composite material has no Fe peak, which shows that all Fe is removed, and finally the porous graphite material is obtained.
Example 2
The embodiment provides an anode material, which is prepared by the following method:
(1) mixing Fe (NO) 3 ) 3 (0.4g) and graphite (0.08g) were mixed thoroughly under an argon atmosphere, the mixture was transferred to an ampoule and evacuated for 35 min. Then, the ampoule is sealed and kept in air at 5 ℃/minHeating to 400 deg.C at heating rate, maintaining the temperature for 24 hr, cooling, and washing with ethanol to remove excessive Fe (NO) 3 ) 3 And dried at 60 ℃ to obtain Fe (NO) 3 ) 3 -GIC；
(2) Fe (NO) to be synthesized 3 ) 3 GIC was transferred to a polypropylene container and irradiated in a microwave oven at 720W for 30s to obtain Fe 2 O 3 -GIC of said Fe 2 O 3 -reducing GIC for 1h at 1020 ℃ in a nitrogen atmosphere, and cooling to obtain Fe-GIC;
(3) transfer of Fe-GIC to Dilute hydrochloric acid (HCl/H) 2 O ═ 1:10) solution, the mixture was stirred and heated at 105 ℃ for 1 h. Then, it was sonicated for 10min and filtered. And repeating the steps for three times, and performing vacuum drying at 60 ℃ for 12 hours to obtain the cathode material.
Example 3
The present example is different from example 1 only in that the mass ratio of the template to graphite is 0.5:1, and other conditions and parameters are exactly the same as those of example 1.
Example 4
The present example is different from example 1 only in that the mass ratio of the template to graphite is 12:1, and other conditions and parameters are completely the same as those of example 1.
Example 5
The present embodiment is different from embodiment 1 only in that the microwave oven in step (2) has a power of 550W, and other conditions and parameters are completely the same as those of embodiment 1.
Example 6
This example is different from example 1 only in that the microwave oven power in step (2) is 850W, and other conditions and parameters are exactly the same as those in example 1.
Comparative example 1
This comparative example used graphite as the negative electrode material.
Comparative example 2
This comparative example employed a conventional porous carbon-based composite (Si/C) as the negative electrode material.
And (3) performance testing:
taking example 1 to treat FeCl after 20s by microwave 3 -GIC、Fe 2 O 3 SEM test of-GIC, Fe-GIC and cathode material, FeCl after microwave treatment for 20s 3 SEM picture of-GIC as shown in FIGS. 2-3, Fe 2 O 3 SEM pictures of-GIC are shown in FIGS. 4-5, Fe-GIC are shown in FIGS. 6-7, and SEM pictures of anode material are shown in FIG. 8, from FIGS. 2-8, it can be seen that FeCl 3 GIC was largely destroyed in the graphite layer structure after 20s of microwave treatment, Fe 2 O 3 The particles were dispersed on the surface and between the layers of the graphite material (FIGS. 2-3), and more Fe was observed on the graphite surface after microwave treatment for 30s 2 O 3 Particles, which indicate that more Fe is produced 2 O 3 (FIGS. 4-5). After the sample was reduced, some pore structure was observed in the graphite layer (FIGS. 6-7), and after the iron particles were washed with acid, pore structure was observed on the graphite surface and in the graphite. The above structure shows that porous graphite materials can be successfully prepared by the strategy.
Testing electrochemical performance: a negative electrode material was prepared by mixing 80 wt% of the prepared material, 10 wt% of acetylene black, and 10 wt% of polyvinylidene fluoride with N-methylpyrrolidone as a solvent. The resulting slurry was then cast onto copper foil and dried in a vacuum oven at 100 ℃ for 24 hours with a mass loading of the electrode of about 1.26mg cm -2 . CR2016 coin cell was assembled in an argon-filled glove box with oxygen and moisture levels below 0.1 ppm. The electrolyte is LiPF containing porous polypropylene 6 (1mol L -1 ) (dimethyl carbonate (DMC)/Ethylene Carbonate (EC) (V DMC: V EC ═ 1:1), and a lithium sheet was used as a counter electrode. Electrochemical performance was measured using a LAND-CT2001A cell tester over a voltage range between 0.01 and 2.0V, with the results shown in Table 1:
TABLE 1
As can be seen from table 1, in examples 1 to 6, the first-time discharge gram capacity of the battery made of the negative electrode material of the present invention can be up to 363.4mAh/g, the second-time discharge gram capacity can be up to 239.2mAh/g, and the capacity retention rate can be up to 65.8%, and by adjusting the material ratio and the reaction conditions during the preparation process, the first-time discharge gram capacity of the battery can be up to 392mAh/g, the second-time discharge gram capacity can be up to 313.8mAh/g, and the capacity retention rate can be up to 65.8%.
Compared with the embodiment 1 and the embodiment 3-4, in the preparation process of the negative electrode material, the mass ratio of the template material to the graphite influences the performance of the prepared negative electrode material, the mass ratio of the template material to the graphite is controlled to be (1-10): 1, the performance of the prepared negative electrode material is good, if the addition amount of the template material is too large, pores formed in the graphite material are too large, the layered structure of the graphite material is damaged, the storage capacity of lithium ions is reduced, the capacity is reduced, and the electrode performance is reduced on the contrary. If the addition amount of the template material is too small, the density of pores formed in the graphite material is low, the capacity of the graphite material is almost unchanged, and the electrode performance is not obviously improved.
Compared with the examples 5 to 6, in the preparation process of the negative electrode material, the performance of the prepared negative electrode material is influenced by the power of microwave treatment, the performance of the prepared negative electrode material is better by controlling the power of the microwave treatment to be 600-800W, and if the power of the microwave treatment is too low, FeCl is added 3 Is difficult to be converted into Fe 2 CO 3 After subsequent treatment, the graphite electrode is difficult to form a pore structure, the performance of the prepared negative electrode material is not obviously affected, and if the power of microwave treatment is too high, the layered structure of the graphite is rapidly destroyed, and the performance of the prepared negative electrode material is rapidly reduced.
The specific capacity of the negative electrode material of example 1 is plotted against the cycle number as shown in fig. 9, the specific capacity of the negative electrode material of comparative example 1 is plotted against the cycle number as shown in fig. 10, and the comparison between example 1 and comparative example 1 shows that the porous graphite material prepared by the invention uses the hard template and successfully replaces the traditional commercial graphite material to be used as the negative electrode material of the lithium ion battery, the porous structure is favorable for the permeation of the electrolyte, thereby leading to the increase of the contact area between the electrode and the electrolyte, and the small particle size provides a shorter diffusion path for lithium ions in the de-intercalation/intercalation process and improving the transmission rate of the lithium ions.
Compared with the comparative example 2, the embodiment 1 can obtain that the conventional porous carbon-based composite material has the advantages of large specific surface area, high pore volume and the like, but generally has the defects of wide pore size distribution, poor conductivity, low mass transmission rate and unstable structure, and the defects greatly hinder the development of the porous carbon material in the electrochemical field.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a negative electrode material is characterized by comprising the following steps:
(1) mixing the template material and graphite, and heating for reaction to obtain a template material-graphite intercalation compound;
(2) transferring the template material-graphite intercalation compound obtained in the step (1) into a container, performing microwave treatment to obtain a metal oxide-graphite intercalation compound, and reducing the metal oxide-graphite intercalation compound to obtain a metal-graphite intercalation compound;
(3) and (3) mixing the metal-graphite intercalation compound obtained in the step (2) with an acid solution, and stirring for reaction to obtain the negative electrode material.
2. The method of claim 1, wherein the template material of step (1) comprises FeCl 3 、FeCl 2 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 、CuCl 2 Or Mn (NO) 3 ) 2 Any one or a combination of at least two of;
preferably, the mass ratio of the template material to the graphite is (1-10): 1.
3. The method according to claim 1 or 2, wherein the mixed atmosphere in the step (1) is an inert atmosphere;
preferably, the means for heating the reaction comprises an ampoule;
preferably, before the heating reaction, vacuumizing is carried out for 25-40 min;
preferably, the heating rate of the heating reaction is 4-6 ℃/min;
preferably, the temperature of the heating reaction is 350-450 ℃;
preferably, the heating reaction time is 20-30 h;
preferably, the heating reaction is followed by cooling, washing and drying;
preferably, the washing detergent comprises ethanol.
4. The method according to any one of claims 1 to 3, wherein the microwave treatment apparatus of step (2) comprises a microwave oven;
preferably, the power of the microwave treatment is 600-800W;
preferably, the microwave treatment time is 25-35 s.
5. The method according to any one of claims 1 to 4, wherein the reducing atmosphere in the step (2) is an inert atmosphere;
preferably, the inert atmosphere comprises nitrogen;
preferably, the temperature of the reduction is 900-1100 ℃;
preferably, the reduction time is 0.5-1.5 h;
preferably, the reduction is followed by a cooling treatment.
6. The method according to any one of claims 1 to 5, wherein the acid solution of step (3) comprises dilute hydrochloric acid;
preferably, the mass ratio of the hydrogen chloride to the water in the dilute hydrochloric acid is (0.5-1.5): 10.
7. The method according to any one of claims 1 to 5, wherein the temperature of the stirring reaction in the step (3) is 90 to 110 ℃;
preferably, the stirring reaction time is 0.5-1.5 h;
preferably, the stirring reaction is followed by sonication and filtration;
preferably, the time of ultrasonic treatment is 5-15 min;
preferably, the step (3) is repeated for 2-3 times;
preferably, vacuum drying is performed after filtration;
preferably, the temperature of the vacuum drying is 50-70 ℃;
preferably, the vacuum drying time is 10-15 h.
8. A negative electrode material, characterized in that it is produced by the method according to any one of claims 1 to 7.
9. A negative electrode tab, characterized in that it comprises the negative electrode material of claim 8.
10. A lithium ion battery comprising the negative electrode tab of claim 9.
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| CN202210441218.5A CN114853004A (en) | 2022-04-25 | 2022-04-25 | Negative electrode material and preparation method and application thereof |
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