CN111293301A - Soft and hard carbon composite porous negative electrode material for sodium ion battery and preparation method thereof - Google Patents
Soft and hard carbon composite porous negative electrode material for sodium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a soft and hard carbon composite porous negative electrode material for a sodium ion battery and a preparation method thereof. The soft and hard carbon composite porous negative electrode material is prepared by regulating and controlling cobalt nitrate, dimethyl imidazole and polyvinyl alcohol. The preparation method comprises the following steps: dropwise adding the ethanol solution of dimethyl imidazole into the ethanol solution of cobalt nitrate, and stirring at room temperature until a precursor ZIF-67 solution is formed; and then adding polyvinyl alcohol into the solution, refluxing to form gel, naturally cooling, freeze-drying, and then placing in an inert gas atmosphere at 700-1100 ℃ for 2-5 hours to obtain the cathode material. The composite negative electrode material prepared by the invention combines the advantages of excellent conductivity of soft carbon and high capacity of hard carbon, effectively improves the stability of the battery, and improves the cycle performance and coulombic efficiency of the sodium ion battery. The method has the advantages of stable raw material components, simple process operation, high repeatability and contribution to industrial production.
Description
Technical Field
The invention relates to a soft and hard carbon composite porous negative electrode material for a sodium ion battery and a preparation method thereof, belonging to the technical field of new materials.
Background
In recent years, rechargeable Lithium Ion Batteries (LIBs) have become the mainstream of electrochemical energy storage devices due to their high energy density and long service life, and play an important role in the fields of smart grids, electric vehicles, personal electronic devices, and the like. However, due to the problems of scarcity of lithium resources, high safety, etc., people are still looking for better substitutes [ Nano lett.,2012,12,3783.]. In contrast, sodium resources are less expensive and rechargeable Sodium Ion Batteries (SIBs) have similar chemical/electrochemical properties to established lithium ion batteries, so they can replace Lithium Ion Batteries (LIBs) and lead acid batteries for large-scale energy storage devices [ j.electrochem.soc.,2019,166, a1096-a 1102; ACS appl. energy mater, 2018,10,30417.]. However, the development of high performance SIBs and their widespread use is much slower than LIB, mainly because of Na+Radius ratio of ion Li+Ion size
Result in Na+Slow migration [ adv.sci.,2015,2, 1500195; matter chem.a.,2018,6,11488.]Designing and developing suitable SIB electrode materials (especially negative electrode materials) is more challenging than LIB. In summary, the development of an anode material with good cycling and rate performance is crucial for the practical application of SIBs.
The carbon-based material has the advantages of wide source, abundant resources, various structures, long service life and the like, so that the carbon-based material becomes a first-choice target for researching sodium storage negative electrode materials [ Nano Res, 2017,10,4378 ].]. Among them, the graphite material is difficult to form a sodium-intercalated graphite compound as a negative electrode material of a sodium ion battery, and only a small amount of Na is contained+Can be stored in graphite, resulting in suppressed reversible capacity (≈ 30mA hg)-1)[Nat.Rev.Mater.,2018,3,18013.]. Non-graphitizing hard carbons, in contrast to graphiteAnd graphitizable soft carbon as the anode material of SIB, have attracted most attention of researchers [ j.mater.chem.a,2018,6,6183.]. Wherein, the hard carbon layer has large spacing, more defects and vacancies and higher sodium storage capacity. In general, Na+The process of inserting hard carbon can be divided into two parts of a slope area and a platform area, wherein (A) in the slope area>0.1V vs.Na/Na+) Electrochemical process is slow due to diffusion of ions in solid phase, Na+Exhibit rapid transport kinetics, the main storage mode being sodium metal adsorption (deposition) on pores or defects [ j.]Therefore, the capacity of the ramp region can be increased by increasing the structural defect sites. However, the more defects, the lower the ionic/electronic conductivity, the poorer the electrochemical stability, which amplifies the drawbacks of hard sodium carbonate [ electrochem.]. In addition, the extremely low potential plateau of hard carbon causes sodium dendrite formation, which presents a safety problem.
Compared with hard carbon that is not graphitizable, graphitizable soft carbon has a smaller lattice spacing and is more difficult to intercalate and deintercalate sodium ions [ electrochim. acta, 2019,304,192 ]; ACS appl.mater.inter, 2015,7, 27124; chem. mater, 2017,29,2314], so the capacity of soft carbon as a negative electrode material for sodium ion batteries is inferior to that of hard carbon.
In addition, soft carbon and hard carbon negative electrode materials also have poor cycle stability, rate capability, reversibility and the like.
Disclosure of Invention
The invention aims to provide a soft and hard carbon composite porous negative electrode material for a sodium ion battery.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
the soft and hard carbon composite porous negative electrode material for the sodium ion battery is prepared from cobalt nitrate (Co (NO)3)2·6H2O), dimethylimidazole (2-MIM) and polyvinyl alcohol (PVA), wherein the mass of the PVA is 2-6 times of the sum of the mass of the cobalt nitrate and the mass of the dimethylimidazole, and the molar ratio of the cobalt nitrate to the dimethylimidazole is 1: 33.
The invention also aims to provide a preparation method of the soft and hard carbon composite porous negative electrode material for the sodium ion battery. The specific technical scheme is as follows:
the preparation method of the soft and hard carbon composite porous negative electrode material for the sodium ion battery comprises the following steps:
dropwise adding an ethanol solution containing dimethyl imidazole into an ethanol solution containing cobalt nitrate, and stirring at room temperature until a precursor ZIF-67 solution is formed; and then adding polyvinyl alcohol with the mass sum of 2-6 times of that of the cobalt nitrate and the dimethyl imidazole into the solution, refluxing at 80-85 ℃ to form gel, naturally cooling, freeze-drying, and then placing in an inert gas atmosphere at 700-1100 ℃ for 2-5 hours to obtain the soft-hard carbon composite porous negative electrode material for the sodium ion battery.
Preferably, the refluxing time is 1-4 h.
Preferably, the concentration of the ethanol solution of the dimethyl imidazole is 15-1.6 g/L, and the concentration of the ethanol solution of the cobalt nitrate is 1.6-15 g/L.
Preferably, the stirring time is 10-60 min.
Preferably, the temperature of the freeze drying is-50 to-70 ℃, and the time is 8 to 16 hours.
The invention has the advantages and beneficial effects that:
according to the invention, a soft carbon source metal organic framework ZIF-67 is synthesized, then a hard carbon source PVA is added to form gel, and a final product is obtained after heat treatment. During the heat treatment process, the ZIF-67 in the gel is graphitized, and the composite porous material with soft and hard carbon phases combined is generated. The soft carbon (graphitized carbon) is used as an electron transport layer, so that the conduction of electrons can be effectively accelerated, and the rate capability of the material is improved; the hard carbon material is used as a sodium storage matrix, and is beneficial to sodium ion desorption. The material has larger specific surface area, abundant micropore and mesoporous structures and larger carbon lattice spacing, and the special microstructure enables the composite material to show good long-cycle performance and rate capability when being applied to a sodium ion battery.
The carbon sources adopted by the invention are ZIF-67 (soft carbon) and PVA (hard carbon), and the method has the advantages of environmental friendliness, wide sources, low price, easy obtainment and the like. The invention adopts a solution method, a gel method and a heat treatment method to synthesize a final product. The preparation method is simple, easy to operate, high in safety and suitable for large-scale production, and large-scale equipment and harsh reaction conditions are not required.
The soft and hard carbon composite porous negative electrode material prepared by the invention has the advantages of excellent conductivity of soft carbon (graphite carbon) and high capacity of hard carbon (non-graphite carbon), is applied to a negative electrode material of a sodium ion battery, and has the characteristics of high first-turn coulombic efficiency, large specific capacity, good cycling stability and the like.
Drawings
FIG. 1 is an X-ray diffraction analysis chart of negative electrode materials for sodium ion batteries prepared in examples 1 to 3 of the present invention; in the figure, the example 1 is soft carbon, the example 2 is soft carbon, and the example 3 is hard carbon;
fig. 2 is an SEM image of the soft and hard carbon composite porous anode material for a sodium ion battery prepared in example 1 of the present invention; (ii) a
Fig. 3 is an SEM image of the soft carbon anode material for sodium ion battery prepared in example 2 of the present invention;
fig. 4 is an SEM image of a hard carbon negative electrode material for a sodium ion battery prepared in example 3 of the present invention;
fig. 5 is a nitrogen adsorption and desorption curve and a pore size distribution diagram of the soft and hard carbon composite porous anode material for a sodium ion battery prepared in example 1 of the present invention.
Fig. 6 is a CV diagram of the soft and hard carbon composite porous anode material for a sodium ion battery prepared in example 1 of the present invention.
Fig. 7 is a charge-discharge diagram of the soft-hard carbon composite porous negative electrode material for the sodium ion battery prepared in example 1 of the present invention.
FIG. 8 shows that the amount of the soft and hard carbon composite porous negative electrode material for sodium ion battery prepared in example 1 of the present invention is 500mA g-1Cycling plot at current density.
Fig. 9 is a performance diagram of the soft and hard carbon composite porous anode material for the sodium ion battery prepared in example 1 of the present invention at different rates.
Detailed Description
The present invention will be further described with reference to the drawings and examples, but the present invention is not limited to the examples.
Example 1
Preparation of soft and hard carbon composite porous negative electrode material for sodium ion battery
60mL of an ethanol solution of dimethylimidazole (containing 930mg of dimethylimidazole) is dropwise added into 60mL of an ethanol solution of cobalt nitrate (containing 100mg of cobalt nitrate), and the mixture is rapidly stirred at room temperature for 30min to obtain a precursor (ZIF-67) solution. And adding 5g of polyvinyl alcohol into the precursor solution, refluxing for 2h at 85 ℃ to form gel, naturally cooling, freeze-drying for 12h at-60 ℃, and then performing heat treatment for 4h in an inert gas atmosphere at 1000 ℃ to obtain the soft and hard carbon composite porous negative electrode material for the sodium ion battery. As can be seen from fig. 1, the X-ray diffraction (XRD) pattern of the soft and hard carbon composite porous negative electrode material prepared in example 1 shows that the peak shape of the composite material is between that of pure soft and hard carbon, indicating that the graphitization degree is between that of soft and hard carbon, and a certain graphitization degree is beneficial to enhancing the electrical conductivity thereof. The diffraction peak position is 25.41, the average lattice spacing is 0.40nm, and the expected result is the same as that of the expected result, and the intercalation and deintercalation of sodium ions are facilitated.
As can be seen from fig. 2, a Scanning (SEM) image of the soft and hard carbon composite porous negative electrode material prepared in example 1 shows that a large number of hollow carbon nanotubes are distributed on the surface, and the diameter of the tube is about 50nm, which is beneficial to the transmission of ions and electrons.
From fig. 5, it can be seen that BET and BJH graphs of the soft and hard carbon composite porous anode material prepared in example 1 show that the specific surface area is 589.37m2g-1The mesoporous volume is 1.31m3g-1The micropore volume is 0.030534cm3g-1. The main pore size distribution of the material is around 4.5 nm. The abundant pore structure means that more electrochemical active sites exist, and the electrochemical performance of the porous membrane is favorably improved.
It can be seen from fig. 6 that the CV chart of the soft and hard carbon composite porous anode material prepared in example 1 shows that there are mainly two reduction peaks at 0.56V and 0.33V, respectivelyOne peak represents the process of sodium ion intercalation into the carbon lattice. The peak at 0.56V corresponds to the formation of a Solid Electrolyte Interface (SEI) film, and the larger reduction peak at 0.33V is probably due to the accompanying Na+The insertion of ions activates carbon. In the anode scanning, two oxidation peaks are respectively positioned at 0.26V and 1.50V, and the two oxidation peaks are Na+The resulting peaks are removed from the carbon lattice. The other CV curves except for the first turn are highly overlapping, indicating good reversibility of the electrode.
From fig. 7, it can be seen that the soft and hard carbon composite porous negative electrode material prepared in example 1 is 0.1A g-1The charge-discharge diagram under current density shows an inclined discharge curve, corresponding to the adsorption-intercalation mechanism of sodium storage. Two discharge regions (a slope voltage region and a low potential platform close to 0V) of hard carbon are reserved, the defect of the low potential platform close to 0V is avoided, and the safety problem can be effectively prevented.
From fig. 8, it can be seen that the soft and hard carbon composite porous negative electrode material prepared in example 1 is 0.1A g-1Cycling performance plot at current density. The first turn of coulombic efficiency was higher and the first few turns of capacity fade less due to SEI film formation and irreversible Na+Insertion, it can be seen that the curve is very smooth within 1000 cycles, and the final capacity is maintained at 377mAh g-1It has excellent circulating stability and is far superior to pure soft carbon and hard carbon material.
Fig. 9 shows that the rate performance graph of the soft and hard carbon composite porous material prepared in example 1 shows that the current density is increased from 0.2C to 20C, and the specific capacity retention rate is as high as 50% under the condition that the current density is increased to 100 times, which proves that the material has good rate performance, and the rate performance is far superior to that of pure soft carbon and hard carbon materials.
Example 2
Preparation of soft carbon negative electrode material for sodium ion battery
60mL of an ethanol solution of dimethylimidazole (containing 930mg of dimethylimidazole) was added dropwise to 60mL of an ethanol solution of cobalt nitrate (containing 100mg of cobalt nitrate). And standing the mixed solution for 24h, centrifuging, washing and drying to obtain a precursor ZIF-67. And then placing the precursor ZIF-67 in a magnetic boat, heating to 600 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h in the nitrogen atmosphere, naturally cooling, soaking for 3h by using hydrochloric acid with the mass fraction of 35% to remove residual Co simple substance on the sample, finally washing with deionized water, filtering, and drying to obtain the soft carbon negative electrode material.
It can be seen from fig. 1 that the X-ray diffraction (XRD) pattern of the soft carbon anode material prepared in example 2 shows two diffraction peaks of (002) and (101). It is noted that the (002) peak position is 26.37 °, corresponding to the interlayer distance (d)002Calculated according to bragg's law) is 0.35nm, the interlayer distance is slightly larger than that of graphite (0.335nm), and a smaller interlayer distance may not be able to intercalate sodium ions, but the conductivity is good.
It can be seen from fig. 3 that the Scanning (SEM) image of the soft carbon anode material prepared in example 2 shows that the material has a uniform cubic structure with a ridge length of about 400 nm.
Example 3
Preparation of hard carbon negative electrode material for sodium ion battery
Dissolving 5g of polyvinyl alcohol in 10mL of deionized water, ultrasonically stirring for 30min to uniformly disperse the polyvinyl alcohol, transferring the polyvinyl alcohol to a single-mouth round-bottom flask, refluxing and stirring for 5h at 85 ℃ to form gel, cooling, centrifuging, freeze-drying for 12h at-60 ℃ to obtain a precursor, placing the precursor in a magnetic boat, heating to 1000 ℃ at a heating rate of 2 ℃/min, preserving heat for 4h in a nitrogen atmosphere, and naturally cooling to obtain the hard carbon negative electrode material for the sodium ion battery.
As can be seen from fig. 1, the X-ray diffraction (XRD) pattern of the hard carbon anode material prepared in example 3 shows that the hard carbon exhibits two broad diffraction peaks, indicating an amorphous structure, and the lattice spacing corresponding to the peak at 22.9 ° 2 θ is 0.4nm, which is greater than the lattice spacing of the soft carbon (>0.35nm), facilitating intercalation of sodium ions, whereas a low degree of graphite indicates poor conductivity of the hard carbon material.
Fig. 4 shows that the Scanning (SEM) image of the hard carbon negative electrode material prepared in example 3 shows that the material has a porous structure, the pores have different sizes, and the diameters of the pores are mostly distributed in the range of 100 to 200 nm.
Example 4
Preparation of soft and hard carbon composite porous negative electrode material for sodium ion battery
The same as in example 1, except that the mass of the polyvinyl alcohol was 2g, and the heat treatment temperature was 700 ℃.
Compared with pure soft carbon and hard carbon materials, SEM shows that a small amount of carbon nanotubes are distributed on the surface of the obtained composite material, and BET and BJH show that the specific surface area and the pore size distribution are between those of the soft carbon and the hard carbon.
Example 5
Preparation of soft and hard carbon composite porous negative electrode material for sodium ion battery
The same as in example 1, except that the mass of the polyvinyl alcohol was 2g, and the heat treatment temperature was 1100 ℃.
BET and BJH showed that the specific surface area of the resulting composite material was large and the pore size distribution was rich, compared to pure soft carbon and hard carbon materials, but the morphology was found to have collapsed morphology from SEM, which indicates that the heat treatment temperature was too high and collapse of morphology was detrimental to ion and electron transport.
Example 6
Preparation of soft and hard carbon composite porous negative electrode material for sodium ion battery
The same as in example 1, except that the mass of the polyvinyl alcohol was 2g, and the heat treatment temperature was 900 ℃.
Compared with pure soft carbon and hard carbon materials, the SEM shows that the surface of the obtained composite material is provided with carbon nanotubes, the BET and BJH show that the specific surface area is enlarged, the pore size distribution is widened, and the electrochemical active sites are increased.
Example 7
Preparation of soft and hard carbon composite porous negative electrode material for sodium ion battery
The same as in example 1, except that the mass of the polyvinyl alcohol was 2g, and the heat treatment temperature was 1000 ℃.
Compared with pure soft carbon and hard carbon materials, SEM shows that the surface of the obtained composite material is uniformly distributed with carbon nano tubes, BET and BJH show that the specific surface area and the pore size distribution are improved and are not much different from those of example 6, but comparison of electrochemical properties shows that 1000 ℃ is the optimal temperature for heat treatment.
Example 8
Preparation of soft and hard carbon composite porous negative electrode material for sodium ion battery
The same as in example 1, except that the mass of the polyvinyl alcohol was 4 g.
BET and BJH showed a great improvement in both specific surface area and pore size distribution compared to the pure soft carbon/hard carbon material, and SEM showed fewer carbon nanotubes on the surface of the material compared to the composite material obtained in example 1, resulting in poor cycle performance.
Example 9
Preparation of soft and hard carbon composite porous negative electrode material for sodium ion battery
The same as in example 1, except that the mass of the polyvinyl alcohol was 6g, and the heat treatment temperature was 1000 ℃.
Compared with a pure soft carbon/hard carbon material, BET and BJH show that the specific surface area and the pore size distribution are greatly improved, SEM shows that the distribution of carbon nanotubes on the surface of the material is not greatly different, and BJH shows that the pore size distribution of the material is not rich, so that the specific capacity is lower.
In addition to the above embodiments, the present invention may have other embodiments, and any technical solutions formed by equivalent substitutions or equivalent transformations fall within the scope of the claims of the present invention.
Claims (6)
1. The soft and hard carbon composite porous negative electrode material for the sodium ion battery is characterized by being prepared from cobalt nitrate, dimethyl imidazole and polyvinyl alcohol, wherein the mass of the polyvinyl alcohol is 2-6 times of the sum of the mass of the cobalt nitrate and the mass of the dimethyl imidazole, and the molar ratio of the cobalt nitrate to the dimethyl imidazole is 1: 33.
2. The preparation method of the soft-hard carbon composite porous anode material for the sodium-ion battery as claimed in claim 1, characterized by comprising the following steps: dropwise adding an ethanol solution containing dimethyl imidazole into an ethanol solution containing cobalt nitrate, and stirring at room temperature until a precursor ZIF-67 solution is formed; and then adding polyvinyl alcohol with the mass sum of 2-6 times of that of the cobalt nitrate and the dimethyl imidazole into the solution, refluxing at 80-85 ℃ to form gel, naturally cooling, freeze-drying, and then placing in an inert gas atmosphere at 700-1100 ℃ for 2-5 hours to obtain the soft-hard carbon composite porous negative electrode material for the sodium ion battery.
3. The preparation method of the soft-hard carbon composite porous anode material for the sodium ion battery according to claim 2, wherein the refluxing time is 1-4 h.
4. The preparation method of the soft-hard carbon composite porous anode material for the sodium-ion battery according to claim 2, wherein the concentration of the ethanol solution of dimethylimidazole is 15-1.6 g/L, and the concentration of the ethanol solution of cobalt nitrate is 1.6-15 g/L.
5. The preparation method of the soft-hard carbon composite porous negative electrode material for the sodium-ion battery according to claim 2, wherein the stirring time is 10-60 min.
6. The preparation method of the soft and hard carbon composite porous negative electrode material for the sodium ion battery according to claim 2, wherein the freeze drying temperature is-50 to-70 ℃ and the time is 8 to 16 hours.
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| CN115321511B (en) * | 2022-08-17 | 2023-11-28 | 合肥霏润新能源技术有限公司 | Porous carbon material and preparation method and application thereof |
| CN115353091B (en) * | 2022-08-17 | 2023-12-08 | 广东东岛新能源股份有限公司 | Hard carbon negative electrode material and preparation method and application thereof |
| CN116613320A (en) * | 2023-06-30 | 2023-08-18 | 湖北万润新能源科技股份有限公司 | Soft carbon and hard carbon co-coated sodium vanadium phosphate positive electrode material, and preparation method and application thereof |
| CN116675216A (en) * | 2023-07-03 | 2023-09-01 | 西北工业大学 | Preparation method of composite hard carbon and application of composite hard carbon in sodium ion battery |
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