CN114497513A - Graphene negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Graphene negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a graphene negative electrode material for a lithium ion battery and a preparation method thereof, wherein the graphene negative electrode material is prepared from the following raw materials: nitrogen-doped porous graphene/SiOxCo-MOFs and emulsified asphalt, and the lithium ion battery prepared by the graphene negative electrode material has higher first charge specific capacity and first charge-discharge capacityThe electric efficiency and the capacity retention rate after 500 cycles can reach more than 83 percent.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a graphene negative electrode material for a lithium ion battery and a preparation method thereof.
Background
In recent years, the rapid development of lithium ion battery technology has been widely applied to the fields of portable electronic equipment, new energy vehicles, power energy storage and the like, and the key for developing the lithium ion battery with high capacity and long service life is to break through the bottleneck of the existing electrode material. The negative electrode material is a carrier of lithium ions and electrons, plays a role in storing and releasing energy, and is an important component of the battery. Therefore, the electrochemical properties of the anode material also determine the performance of the battery to some extent. The cathode material of the current commercial lithium ion battery is mainly a carbon material, and the carbon material has the advantages of rich raw materials, low electrode potential, low price, no toxicity, stability and the like, and can effectively solve the potential safety hazard caused by dendritic crystal generated by a metal lithium cathode. However, the theoretical capacity of the commercial graphite negative electrode is only 372mAh/g, and the target of high energy density of a new generation of lithium battery is difficult to achieve, so the research and development of a novel high-capacity lithium ion battery negative electrode material are urgent.
Graphene has been widely studied as an electrode material because of its ultra-high specific surface area, excellent electrical conductivity, excellent mechanical strength, and chemical stability. However, since graphene alone has a disadvantage of rapid capacity fade as a negative electrode material and is difficult to be used as an electrode material as it is, it is possible to obtain an ideal negative electrode material for a lithium ion battery by compounding graphene with other materials to form an electrode material and by fully utilizing the excellent characteristics of the electrode material.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical development trend, the invention provides a graphene negative electrode material for a lithium ion battery and a preparation method thereof.
The adopted technical scheme is as follows:
the graphene negative electrode material for the lithium ion battery is characterized by being prepared from the following raw materials: nitrogen-doped porous graphene/SiOxCo-MOFs, emulsified asphalt.
Further, the nitrogen-doped porous graphene/SiOxThe mass ratio of Co-MOFs is 1-5: 1-5.
Further, the nitrogen-doped porous graphene/SiOxThe preparation method comprises the following steps:
mixing porous graphene/SiOxDispersing in ammonia water, transferring to a hydrothermal reaction kettle, reacting at 160-180 ℃ for 8-12h, centrifuging, washing the obtained solid to neutrality, and drying.
Further, the porous graphene/SiOxThe preparation method comprises the following steps:
s1: ultrasonically dispersing graphene oxide in water, adding hydrogen peroxide, uniformly stirring, transferring the mixed solution into a hydrothermal reaction kettle, reacting at 160-180 ℃ for 4-6h, centrifuging, and washing the obtained solid to be neutral to obtain graphene oxide powder;
s2: under the protection of argon, carrying out disproportionation treatment on SiO at 1050 ℃ for 3-5h at 1000-xPowder;
s3: mixing starch, graphene oxide powder and SiOxAdding the powder into PVA solution, mixing and stirring uniformly, granulating, roasting the obtained granules at the temperature of 550-600 ℃ for 2-5h, cooling along with the furnace, and grinding to obtain the porous graphene/SiOx。
Further, the starch, the graphene oxide powder and the SiOxThe mass ratio of the powder is 1: 20-40: 5-10.
Further, the preparation method of the Co-MOFs is as follows:
mixing cobalt acetate and H3TATAB is added into a mixed solution composed of ethanol and DMF, the mixture is transferred into a hydrothermal reaction kettle and reacts for 36 to 48 hours at the temperature of 160-180 ℃, and the mixture is centrifuged and dried.
Further, the cobalt acetate and H3The molar ratio of TATAB is 1: 2.
further, the preparation method of the emulsified asphalt comprises the following steps:
adding asphalt into a mixed solution composed of styrene and acrylonitrile, uniformly stirring, adding an emulsifier solution, shearing for 30-60min by using a high-speed shearing machine, and standing for 10-15h for ultrasonic defoaming.
Further, the emulsifier solution comprises the following components in parts by weight:
2-3 parts of sodium dodecyl benzene sulfonate, 800.5-1 parts of tween, 5-10 parts of sodium polyacrylate, 40-45 parts of disproportionated potassium rosinate and 300 parts of water 250-one.
The invention also provides a preparation method of the graphene negative electrode material for the lithium ion battery, which comprises the following steps:
doping nitrogen with porous graphene/SiOxAdding Co-MOFs into emulsified asphalt, performing ultrasonic oscillation for 10-20min, performing vacuum impregnation for 3-5h, performing reduced pressure distillation to remove the solvent, roasting at 900-950 ℃ for 2-4h, cooling in a furnace to room temperature, and grinding the obtained solidAnd (4) homogenizing.
The invention has the beneficial effects that:
the silicon-based oxide has high specific capacity and good cycle performance, and Li is in the primary lithiation process+With SiOxReaction-generated Li2O and Li4SO4Can be used as a buffer substance to adjust the volume change caused by silicon-lithium alloying, thereby improving the cycle performance of the battery, and the surface of the SiO coated with graphenexThe constructed conductive network can further improve the conductivity of the negative electrode material, meanwhile, the porous structure can provide an effective buffer space to inhibit the volume expansion of the electrode in the charging and discharging processes, due to the introduction of heteroatom nitrogen, the surface disorder of graphene is increased, the wettability of the electrode-electrolyte is optimized, so that the electrochemical performance is improved, and the high specific surface area and the adjustable pore channel of MOFs are favorable for Li (lithium ion) batteries in the charging and discharging processes+According to the invention, organic ligands with longer branched chains and higher nitrogen content are introduced, the prepared Co-MOFs has high nitrogen content, the electronic transmission process between an electrode and an electrolyte can be effectively promoted, the stability of the MOFs is improved due to the introduction of cobalt, emulsified asphalt is used as a binder, particles can be uniformly dispersed, the uniformity of a negative electrode material is improved, and the reduction of conductivity caused by particle agglomeration is reduced.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
a preparation method of a graphene negative electrode material for a lithium ion battery comprises the following steps:
grinding 10g of graphene oxide into powder, ultrasonically dispersing the powder in 100mL of water, adding 15mL of hydrogen peroxide, uniformly stirring, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 6h at 180 ℃,centrifuging, washing the obtained solid to be neutral to obtain graphene oxide powder, under the protection of argon, placing 10g of SiO in an annealing furnace, carrying out disproportionation treatment at 1050 ℃ for 5 hours, and then cooling along with the furnace to obtain SiOxPowder prepared from starch, graphene oxide powder and SiOxThe powder comprises the following components in percentage by mass 1: 40: 10 is added into a 7 wt% PVA solution, the mixture is evenly stirred and granulated, the obtained granules are roasted for 5 hours at the temperature of 600 ℃, cooled along with the furnace and ground to obtain the porous graphene/SiOx10g of porous graphene/SiOxDispersing in 500mL of ammonia water, transferring to a hydrothermal reaction kettle, reacting at 180 ℃ for 12h, centrifuging, washing the obtained solid to be neutral, and drying to obtain the nitrogen-doped porous graphene/SiOxFor standby, 5g of cobalt acetate and H3TATAB (2,4, 6-tris [ (p-carboxyphenyl) amino group)]-1,3, 5-triazine) 19.5g is added into 200mL of mixed solution consisting of ethanol and DMF (N, N-dimethylformamide) according to the volume ratio of 1:1, the mixed solution is transferred into a hydrothermal reaction kettle, the mixture is reacted for 48h at 180 ℃, the centrifugation and the drying are carried out to obtain Co-MOFs for standby application, 1.5g of sodium dodecyl benzene sulfonate, 800.5 g of Tween, 5g of sodium polyacrylate, 22.5g of disproportionated potassium rosinate and 150g of water are mixed and stirred uniformly to obtain emulsifier solution, 20g of asphalt is added into the mixed solution consisting of 15mL of styrene and 15mL of acrylonitrile, the emulsifier solution is added after the stirring is uniform, the mixture is sheared for 60min by a high-speed shearing machine and is kept stand for 15h for ultrasonic defoaming to obtain emulsified asphalt, and the nitrogen-doped porous graphene/SiOxAdding 10g of Co-MOFs and 10g of Co-MOFs into the emulsified asphalt, carrying out ultrasonic oscillation for 20min, carrying out vacuum impregnation for 5h, carrying out reduced pressure distillation to remove the solvent, roasting at 900 ℃ for 2h, cooling the furnace to room temperature, and grinding the obtained solid uniformly.
Example 2:
a preparation method of a graphene negative electrode material for a lithium ion battery comprises the following steps:
grinding 10g of graphene oxide into powder, ultrasonically dispersing the powder in 100mL of water, adding 15mL of hydrogen peroxide, uniformly stirring, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 4 hours at 160 ℃, centrifuging, washing the obtained solid to be neutral to obtain graphene oxide powder, placing 10g of SiO in an annealing furnace under the protection of argon, carrying out disproportionation treatment at 1000 ℃ for 3 hours, and cooling along with the furnace to obtain SiOxPowder prepared from starch and graphene oxidePowder, SiOxThe powder comprises the following components in percentage by mass 1: 20: 5, adding the mixture into a 7 wt% PVA solution, uniformly mixing and stirring, granulating, roasting the obtained granules at 550 ℃ for 2 hours, cooling along with a furnace, and grinding to obtain the porous graphene/SiOx10g of porous graphene/SiOxDispersing in 500mL of ammonia water, transferring to a hydrothermal reaction kettle, reacting at 160 ℃ for 8h, centrifuging, washing the obtained solid to be neutral, and drying to obtain the nitrogen-doped porous graphene/SiOxFor standby, 5g of cobalt acetate and H3TATAB (2,4, 6-tris [ (p-carboxyphenyl) amino group)]-1,3, 5-triazine) 19.5g is added into 200mL of mixed solution composed of ethanol and DMF (N, N-dimethylformamide) according to the volume ratio of 1:1, the mixed solution is transferred into a hydrothermal reaction kettle, the mixture is reacted for 36h at 160 ℃, the centrifugation and the drying are carried out to obtain Co-MOFs for standby use, 1g of sodium dodecyl benzene sulfonate, 800.25 g of Tween, 2.5g of sodium polyacrylate, 20g of disproportionated potassium rosinate and 125g of water are mixed and stirred uniformly to obtain emulsifier solution, 20g of asphalt is added into the mixed solution composed of 15mL of styrene and 15mL of acrylonitrile, the emulsifier solution is added after the stirring is uniform, the mixture is sheared for 30min by a high-speed shearing machine and then is kept stand for 10h for ultrasonic defoaming to obtain emulsified asphalt, and nitrogen-doped porous graphene/SiOxAdding 10g and 8g of Co-MOFs into the emulsified asphalt, carrying out ultrasonic oscillation for 10min, carrying out vacuum impregnation for 3h, carrying out reduced pressure distillation to remove the solvent, roasting at 950 ℃ for 3h, cooling in a furnace to room temperature, and grinding the obtained solid uniformly.
Example 3:
a preparation method of a graphene negative electrode material for a lithium ion battery comprises the following steps:
grinding 10g of graphene oxide into powder, ultrasonically dispersing the powder in 100mL of water, adding 15mL of hydrogen peroxide, uniformly stirring, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 4 hours at 180 ℃, centrifuging, washing the obtained solid to be neutral to obtain graphene oxide powder, placing 10g of SiO in an annealing furnace under the protection of argon, carrying out disproportionation treatment at 1050 ℃ for 3 hours, and cooling along with the furnace to obtain SiOxPowder prepared from starch, graphene oxide powder and SiOxThe powder comprises the following components in percentage by mass 1: 40: 5, adding the mixture into a 7 wt% PVA solution, uniformly mixing and stirring, granulating, roasting the obtained granules at 600 ℃ for 2 hours, cooling the granules along with a furnace, and grinding the granules to obtain the porous graphene/SiOx10 will beg porous graphene/SiOxDispersing in 500mL of ammonia water, transferring to a hydrothermal reaction kettle, reacting at 180 ℃ for 8h, centrifuging, washing the obtained solid to be neutral, and drying to obtain the nitrogen-doped porous graphene/SiOxFor standby, 5g of cobalt acetate and H3TATAB (2,4, 6-tris [ (p-carboxyphenyl) amino group)]-1,3, 5-triazine) 19.5g is added into 200mL of mixed solution composed of ethanol and DMF (N, N-dimethylformamide) according to the volume ratio of 1:1, the mixed solution is transferred into a hydrothermal reaction kettle, the mixture is reacted for 36h at 180 ℃, the centrifugation and the drying are carried out to obtain Co-MOFs for standby use, 1.5g of sodium dodecyl benzene sulfonate, 800.25 g of Tween, 5g of sodium polyacrylate, 20g of disproportionated potassium rosinate and 150g of water are mixed and stirred uniformly to obtain emulsifier solution, 20g of asphalt is added into the mixed solution composed of 15mL of styrene and 15mL of acrylonitrile, the emulsifier solution is added after the stirring is uniform, the mixture is sheared for 30min by a high-speed shearing machine and is kept stand for 15h for ultrasonic defoaming to obtain emulsified asphalt, and the nitrogen-doped porous graphene/SiOxAdding 10g and 5g of Co-MOFs into the emulsified asphalt, carrying out ultrasonic oscillation for 10min, carrying out vacuum impregnation for 5h, carrying out reduced pressure distillation to remove the solvent, roasting at 950 ℃ for 2h, cooling in a furnace to room temperature, and grinding the obtained solid uniformly.
Example 4:
a preparation method of a graphene negative electrode material for a lithium ion battery comprises the following steps:
grinding 10g of graphene oxide into powder, ultrasonically dispersing the powder in 100mL of water, adding 15mL of hydrogen peroxide, uniformly stirring, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing the obtained solid to be neutral to obtain graphene oxide powder, placing 10g of SiO in an annealing furnace under the protection of argon, carrying out disproportionation treatment at 1000 ℃ for 5 hours, and cooling the obtained solid along with the furnace to obtain SiOxPowder is prepared from starch, graphene oxide powder and SiOxThe powder comprises the following components in percentage by mass 1: 20: 10 is added into a 7 wt% PVA solution, the mixture is evenly stirred and granulated, the obtained granules are roasted for 5 hours at 550 ℃, cooled along with the furnace and ground to obtain the porous graphene/SiOx10g of porous graphene/SiOxDispersing in 500mL of ammonia water, transferring to a hydrothermal reaction kettle, reacting at 160 ℃ for 12h, centrifuging, washing the obtained solid to be neutral, and drying to obtain the nitrogen-doped porous graphene/SiOxFor standby, vinegar is addedCobalt acid 5g and H3TATAB (2,4, 6-tris [ (p-carboxyphenyl) amino group)]-1,3, 5-triazine) 19.5g is added into 200mL of mixed solution consisting of ethanol and DMF (N, N-dimethylformamide) according to the volume ratio of 1:1, the mixed solution is transferred into a hydrothermal reaction kettle, the hydrothermal reaction kettle reacts for 48h at 160 ℃, the centrifugal reaction and the drying are carried out to obtain Co-MOFs for standby application, 1g of sodium dodecyl benzene sulfonate, 800.5 g of Tween, 2.5g of sodium polyacrylate, 22.5g of disproportionated rosin potassium acid and 125g of water are mixed and stirred uniformly to obtain emulsifier solution, 20g of asphalt is added into the mixed solution consisting of 15mL of styrene and 15mL of acrylonitrile, the emulsifier solution is added after the stirring is uniform, the mixture is sheared for 60min by a high-speed shearing machine and then is kept stand for 10h for ultrasonic defoaming to obtain emulsified asphalt, and nitrogen-doped porous graphene/SiO are mixed with waterxAdding 10g of Co-MOFs and 10g of Co-MOFs into the emulsified asphalt, carrying out ultrasonic oscillation for 20min, carrying out vacuum impregnation for 3h, carrying out reduced pressure distillation to remove the solvent, roasting at 950 ℃ for 2h, cooling in a furnace to room temperature, and grinding the obtained solid uniformly.
Example 5:
a preparation method of a graphene negative electrode material for a lithium ion battery comprises the following steps:
grinding 10g of graphene oxide into powder, ultrasonically dispersing the powder in 100mL of water, adding 15mL of hydrogen peroxide, uniformly stirring, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 5 hours at 165 ℃, centrifuging, washing the obtained solid to be neutral to obtain graphene oxide powder, placing 10g of SiO in an annealing furnace under the protection of argon, carrying out disproportionation treatment at 1050 ℃ for 4 hours, and cooling along with the furnace to obtain SiOxPowder prepared from starch, graphene oxide powder and SiOxThe powder comprises the following components in percentage by mass 1: 25: 5 is added into a 7 wt% PVA solution, the mixture is evenly stirred and granulated, the obtained granules are roasted for 4 hours at 580 ℃, cooled along with the furnace and ground to obtain the porous graphene/SiOx10g of porous graphene/SiOxDispersing in 500mL of ammonia water, transferring to a hydrothermal reaction kettle, reacting at 160 ℃ for 10h, centrifuging, washing the obtained solid to be neutral, and drying to obtain the nitrogen-doped porous graphene/SiOxFor standby, 5g of cobalt acetate and H3TATAB (2,4, 6-tris [ (p-carboxyphenyl) amino group)]-1,3, 5-triazine) 19.5g is added into 200mL of a mixed solution of ethanol and DMF (N, N-dimethylformamide) in a volume ratio of 1:1, transferred into a hydrothermal reaction kettle, and reacted at 180 DEG CCentrifuging for 48 hours, drying to obtain Co-MOFs for later use, mixing and uniformly stirring 1g of sodium dodecyl benzene sulfonate, 800.5 g of tween, 3g of sodium polyacrylate, 20g of potassium disproportionated rosin and 125g of water to obtain an emulsifier solution, adding 20g of asphalt into a mixed solution consisting of 15mL of styrene and 15mL of acrylonitrile, uniformly stirring, adding the emulsifier solution, shearing for 50 minutes by using a high-speed shearing machine, standing for 15 hours, ultrasonically defoaming to obtain emulsified asphalt, and mixing nitrogen-doped porous graphene/SiOxAdding 10g of Co-MOFs and 10g of Co-MOFs into the emulsified asphalt, carrying out ultrasonic oscillation for 15min, carrying out vacuum impregnation for 5h, carrying out reduced pressure distillation to remove the solvent, roasting at 950 ℃ for 2h, cooling the furnace to room temperature, and grinding the obtained solid uniformly.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that graphene oxide is used instead of nitrogen-doped porous graphene/SiOx。
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that porous graphene/SiOxWithout nitrogen doping treatment.
Comparative example 3
Comparative example 3 is essentially the same as example 1 except that commercially available ZIF-67 was used in place of the Co-MOFs.
Comparative example 4
Comparative example 4 is essentially the same as example 1 except that no emulsifier solution is added.
And (3) performance testing:
respectively weighing and uniformly mixing the graphene negative electrode material prepared in the embodiments 1-5 and the comparative examples 1-4 of the invention with superconducting carbon and polyacrylic acid according to a mass ratio of 8:1:1, wherein the polyacrylic acid is mixed in a solution form with a mass content of 10%, stirring the mixture into slurry, coating the slurry on a copper foil, drying and cutting into pieces to obtain pole pieces, putting the pole pieces into a glove box, taking a metal lithium piece as a counter electrode, adopting a polypropylene diaphragm, and taking a 1mol/L LiPF6/EC + DEC + EMC solution as an electrolyte, wherein EC is ethylene carbonate, DEC is diethyl carbonate, EMC is ethyl methyl carbonate, and the volume ratio of the three is 1: 1:1, assembling into a CR2032 button cell in a glove box filled with dry argon.
The battery performance test is carried out at 25 +/-2 ℃, and the steps are as follows:
(1)0.1C to 0.005V; (2) standing for 1 min; (3)0.05C to 0.005V; (4) standing for 1 min; (5)0.02C to 0.005V; (6) standing for 1 min; (7)0.1C to 3.0V; (8) standing for 1min, circulating for 500 times according to the steps, and obtaining the battery performance test results of the graphene negative electrode materials in examples 1-5 and comparative examples 1-4 shown in table 1:
table 1:
as can be seen from table 1 above, the lithium ion battery prepared from the graphene negative electrode material has high first charge specific capacity and first charge-discharge efficiency, and the capacity retention rate can reach over 83% after 500 cycles.
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 (10)
1. The graphene negative electrode material for the lithium ion battery is characterized by being prepared from the following raw materials: nitrogen-doped porous graphene/SiOxCo-MOFs, emulsified asphalt.
2. The graphene negative electrode material for a lithium ion battery according to claim 1, wherein the nitrogen-doped porous graphene/SiOxThe mass ratio of Co-MOFs is 1-5: 1-5.
3. The graphene negative electrode material for lithium ion batteries according to claim 1, which isCharacterized in that the nitrogen-doped porous graphene/SiOxThe preparation method comprises the following steps:
mixing porous graphene/SiOxDispersing in ammonia water, transferring to a hydrothermal reaction kettle, reacting at 160-180 ℃ for 8-12h, centrifuging, washing the obtained solid to neutrality, and drying.
4. The graphene negative electrode material for a lithium ion battery according to claim 3, wherein the porous graphene/SiOxThe preparation method comprises the following steps:
s1: ultrasonically dispersing graphene oxide in water, adding hydrogen peroxide, uniformly stirring, transferring the mixed solution into a hydrothermal reaction kettle, reacting at 160-180 ℃ for 4-6h, centrifuging, and washing the obtained solid to be neutral to obtain graphene oxide powder;
s2: under the protection of argon, carrying out disproportionation treatment on SiO at 1050 ℃ for 3-5h at 1000-xPowder;
s3: mixing starch, graphene oxide powder and SiOxAdding the powder into PVA solution, mixing and stirring uniformly, granulating, roasting the obtained granules at the temperature of 550-600 ℃ for 2-5h, cooling along with the furnace, and grinding to obtain the porous graphene/SiOx。
5. The graphene negative electrode material for a lithium ion battery according to claim 4, wherein the starch, the graphene oxide powder, and SiO arexThe mass ratio of the powder is 1: 20-40: 5-10.
6. The graphene anode material for the lithium ion battery according to claim 1, wherein the preparation method of the Co-MOFs is as follows:
mixing cobalt acetate and H3Adding TATAB into a mixed solution consisting of ethanol and DMF, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 36-48h at the temperature of 160-180 ℃, centrifuging and drying.
7. The graphene negative electrode material for a lithium ion battery according to claim 6, wherein the cobalt acetate and H are3The molar ratio of TATAB is 1: 2.
8. the graphene negative electrode material for the lithium ion battery according to claim 1, wherein the preparation method of the emulsified asphalt comprises the following steps:
adding asphalt into mixed solution consisting of styrene and acrylonitrile, stirring uniformly, adding emulsifier solution, shearing by a high-speed shearing machine for 30-60min, and standing for 10-15h for ultrasonic defoaming.
9. The graphene negative electrode material for the lithium ion battery according to claim 8, wherein the emulsifier solution comprises the following components in parts by weight:
2-3 parts of sodium dodecyl benzene sulfonate, 800.5-1 parts of tween, 5-10 parts of sodium polyacrylate, 40-45 parts of disproportionated potassium rosinate and 300 parts of water 250-one.
10. The preparation method of the graphene anode material for the lithium ion battery according to any one of claims 1 to 9, wherein nitrogen is doped into porous graphene/SiOxAnd adding Co-MOFs into the emulsified asphalt, performing ultrasonic oscillation for 10-20min, performing vacuum impregnation for 3-5h, performing reduced pressure distillation to remove the solvent, finally roasting at 900-950 ℃ for 2-4h, cooling in a furnace to room temperature, and uniformly grinding the obtained solid.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906016A (en) * | 2010-04-22 | 2013-01-30 | 巴斯夫欧洲公司 | Method for producing two-dimensional sandwich nano-materials on the basis of graphene |
| CN103180243A (en) * | 2010-12-29 | 2013-06-26 | 海洋王照明科技股份有限公司 | Porous graphene material and preparation method and uses as electrode material thereof |
| CN103449414A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method of graphene having porous structure |
| CN104925794A (en) * | 2015-06-11 | 2015-09-23 | 青岛大学 | Method for growing three-dimensional nitrogen-doped graphene by taking nanoporous graphene as substrate |
| CN105289695A (en) * | 2015-12-08 | 2016-02-03 | 武汉理工大学 | Graphene loaded Co-N-C oxygen reduction catalyst and preparation method thereof |
| CN105384164A (en) * | 2015-12-18 | 2016-03-09 | 上海理工大学 | Crumpled graphene with characteristics of high specific surface area and graded pore structure, and preparation method thereof |
| CN105810945A (en) * | 2016-05-26 | 2016-07-27 | 江苏深苏电子科技有限公司 | Preparation method of lithium ion battery cathode material nitrogen-doped three-dimensional porous graphene |
| CN106898759A (en) * | 2017-04-25 | 2017-06-27 | 张廷祥 | The preparation method and graphene lithium ion battery group of graphene lithium ion battery cathode pole piece |
| CN106935825A (en) * | 2017-03-21 | 2017-07-07 | 桂林电子科技大学 | A kind of graphene oxide/metal organic frame composite and its preparation method and application |
| CN107180954A (en) * | 2017-05-24 | 2017-09-19 | 张廷祥 | A kind of ultra-thin graphite alkene lithium ion single battery and graphene lithium ion battery group |
| CN107732187A (en) * | 2017-09-30 | 2018-02-23 | 乌兰察布市大盛石墨新材料股份有限公司 | Silica graphene composite negative pole and preparation method thereof |
| CN108033440A (en) * | 2018-01-16 | 2018-05-15 | 上海理工大学 | A kind of preparation method of high specific surface area porous fold graphene |
| CN109037615A (en) * | 2018-07-08 | 2018-12-18 | 启东祥瑞建设有限公司 | A kind of preparation method of Cu-MOF/rGO lithium ion battery negative material |
| CN109192532A (en) * | 2018-09-28 | 2019-01-11 | 上海师范大学 | A kind of electrode material for super capacitor and preparation method thereof |
| CN110299530A (en) * | 2019-07-22 | 2019-10-01 | 福州大学 | A kind of ZIF-67 base cobalt molybdenum oxide hollow Nano cage/graphene composite material and the preparation method and application thereof |
| CN111933933A (en) * | 2020-07-31 | 2020-11-13 | 广东凯金新能源科技股份有限公司 | Novel lithium ion battery cathode material and preparation method thereof |
| CN112436126A (en) * | 2020-12-01 | 2021-03-02 | 桐乡市华璟科技有限公司 | Nitrogen-doped graphene-porous CoFe2O4Lithium ion battery cathode material and preparation method thereof |
-
2022
- 2022-03-05 CN CN202210218427.3A patent/CN114497513A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906016A (en) * | 2010-04-22 | 2013-01-30 | 巴斯夫欧洲公司 | Method for producing two-dimensional sandwich nano-materials on the basis of graphene |
| CN103180243A (en) * | 2010-12-29 | 2013-06-26 | 海洋王照明科技股份有限公司 | Porous graphene material and preparation method and uses as electrode material thereof |
| CN103449414A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method of graphene having porous structure |
| CN104925794A (en) * | 2015-06-11 | 2015-09-23 | 青岛大学 | Method for growing three-dimensional nitrogen-doped graphene by taking nanoporous graphene as substrate |
| CN105289695A (en) * | 2015-12-08 | 2016-02-03 | 武汉理工大学 | Graphene loaded Co-N-C oxygen reduction catalyst and preparation method thereof |
| CN105384164A (en) * | 2015-12-18 | 2016-03-09 | 上海理工大学 | Crumpled graphene with characteristics of high specific surface area and graded pore structure, and preparation method thereof |
| CN105810945A (en) * | 2016-05-26 | 2016-07-27 | 江苏深苏电子科技有限公司 | Preparation method of lithium ion battery cathode material nitrogen-doped three-dimensional porous graphene |
| CN106935825A (en) * | 2017-03-21 | 2017-07-07 | 桂林电子科技大学 | A kind of graphene oxide/metal organic frame composite and its preparation method and application |
| CN106898759A (en) * | 2017-04-25 | 2017-06-27 | 张廷祥 | The preparation method and graphene lithium ion battery group of graphene lithium ion battery cathode pole piece |
| CN107180954A (en) * | 2017-05-24 | 2017-09-19 | 张廷祥 | A kind of ultra-thin graphite alkene lithium ion single battery and graphene lithium ion battery group |
| CN107732187A (en) * | 2017-09-30 | 2018-02-23 | 乌兰察布市大盛石墨新材料股份有限公司 | Silica graphene composite negative pole and preparation method thereof |
| CN108033440A (en) * | 2018-01-16 | 2018-05-15 | 上海理工大学 | A kind of preparation method of high specific surface area porous fold graphene |
| CN109037615A (en) * | 2018-07-08 | 2018-12-18 | 启东祥瑞建设有限公司 | A kind of preparation method of Cu-MOF/rGO lithium ion battery negative material |
| CN109192532A (en) * | 2018-09-28 | 2019-01-11 | 上海师范大学 | A kind of electrode material for super capacitor and preparation method thereof |
| CN110299530A (en) * | 2019-07-22 | 2019-10-01 | 福州大学 | A kind of ZIF-67 base cobalt molybdenum oxide hollow Nano cage/graphene composite material and the preparation method and application thereof |
| CN111933933A (en) * | 2020-07-31 | 2020-11-13 | 广东凯金新能源科技股份有限公司 | Novel lithium ion battery cathode material and preparation method thereof |
| CN112436126A (en) * | 2020-12-01 | 2021-03-02 | 桐乡市华璟科技有限公司 | Nitrogen-doped graphene-porous CoFe2O4Lithium ion battery cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李文超 等: "用于锂离子电池的高性能SiOx/C/石墨烯复合负极材料", 《材料导报Ｂ：研究篇》, vol. 31, no. 8, pages 16 * |
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