CN113921823A - CuO/O-g-C3N4Lithium ion battery cathode material and preparation method thereof - Google Patents
CuO/O-g-C3N4Lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 36
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002211 L-ascorbic acid Substances 0.000 claims abstract description 17
- 235000000069 L-ascorbic acid Nutrition 0.000 claims abstract description 17
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000004005 microsphere Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004570 mortar (masonry) Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000005054 agglomeration Methods 0.000 claims description 4
- 230000002776 aggregation Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 3
- 230000000630 rising effect Effects 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 238000011056 performance test Methods 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 50
- 239000000463 material Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Abstract
The invention discloses a CuO/O-g-C3N4The lithium ion battery cathode material is a three-dimensional heterostructure, and CuO microspheres are uniformly dispersed in g-C3N4In a matrix; the invention adopts a thermal polycondensation method to prepare g-C3N4Thereafter, calcining g-C at low temperature3N4And L-ascorbic acid to synthesize oxygen-enriched doped g-C3N4The method is used for modifying the nano structure of the CuO microsphere. Prepared CuO/O-g-C3N4The negative electrode material is used for various physical property tests and electrochemical electrode, battery performance tests and the like. The inventionThrough simple operation steps and mild reaction conditions, the CuO microspheres are dispersed in O-g-C3N4The matrix prevents the CuO from agglomerating, effectively inhibits the volume expansion of the CuO in the charge-discharge process, contributes to improving the charge-discharge efficiency of the cathode and the cycle performance, and obtains the high-stability lithium ion battery cathode material.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery electrode materials, and particularly relates to CuO/O-g-C3N4A lithium ion battery cathode material and a preparation method thereof.
Background
Lithium ion batteries, as one of the most promising energy storage materials, have become a research hotspot in the field of novel energy sources due to the advantages of long cycle life, high energy density, low self-discharge rate, good thermal stability, unobvious memory effect, and the like. At present, commercial lithium ion batteries mainly adopt carbon materials such as artificial graphite and the like as a negative electrode, but due to low theoretical capacity (372mAh/g), the limitations of the traditional electrode materials in the aspects of specific capacity, cycle life and safety are increasingly prominent, and the further development of the lithium ion batteries is restricted.
The lithiation potential platform of copper oxide (CuO) is high, the source is wide, the energy density is high, the theoretical capacity is 778mAh/g, and the comprehensive electrochemical performance is superior to that of the common battery cathode material graphite. However, the lithium storage mechanism of copper oxide is derived from the conversion reaction mechanism of self-lithium-releasing of transition group metal oxide, the insertion process is the conversion from crystalline state to amorphous state, and the volume increase to a large extent in the charge and discharge process has influence on the stability of the lithium battery in the charge and discharge process. Therefore, the research on the electrode material for solving the CuO defect to obtain higher performance energy density and power density has become a problem to be solved.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to provide CuO/O-g-C3N4Lithium ion battery negative electrode material and preparation method thereof, g-C3N4The stability and cycling performance of CuO can be improved because of the large surface area, tunable porous layer structure, and cost-effective availability. Using oxygen-doped g-C3N4(O-g-C3N4) Modified CuOIn one aspect, g-C3N4The intrinsic band structure of (a) can be reduced by oxygen doping, thereby increasing the conductivity. On the other hand, O-g-C due to the presence of C-O-C bonds and N-C-O bonds3N4The interaction between CuO and CuO can be strengthened, which is helpful for avoiding CuO agglomeration. Thus, the CuO microspheres are mixed with O-g-C3N4The combination is beneficial to improving the conductivity of the battery cathode material, thereby playing the dual roles of 'inhibition' and 'conduction'.
In order to achieve the purpose, the invention adopts the technical scheme that:
CuO/O-g-C3N4Lithium ion battery negative electrode material CuO/O-g-C3N4The lithium ion battery cathode material is of a three-dimensional heterostructure, and CuO microspheres are uniformly dispersed in g-C3N4In the matrix, g-C3N4The CuO microsphere has a large surface area and an adjustable porous layer structure, and the intrinsic energy band structure of the CuO microsphere is reduced by oxygen doping, so that the conductivity is improved, the CuO microsphere is in full contact with the electrolyte of a lithium ion battery, CuO agglomeration is prevented, and the volume expansion of CuO in the charging and discharging process is effectively inhibited.
One kind of CuO/O-g-C3N4The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: putting melamine into a crucible with a cover, and calcining in a muffle furnace to obtain a block C3N4；
Step two: the obtained block C3N4Fully grinding the mixture and then carrying out thermal oxidation to obtain powdery g-C3N4；
Step three: the obtained powder g-C3N4Grinding the mixture and L-ascorbic acid in an agate mortar, transferring the mixed powder into a tubular furnace, carrying out thermal reaction in a nitrogen atmosphere, naturally cooling the sample to room temperature after the reaction is finished, and grinding the sample in an agate mortar again to obtain O-g-C3N4；
Step four: mixing O-g-C3N4Dissolving in deionized water, ultrasonic treating, and adding Cu (NO)3)2·3H2Stirring O, and dripping NaOH solution while stirring;
step five: after stirring, collecting the obtained product, carrying out centrifugal washing until the pH value of colorless filtrate reaches neutral, carrying out vacuum drying treatment, and carrying out heat treatment on the dried product to obtain CuO/O-g-C3N4A lithium ion battery cathode material.
Adding 8-10 g of melamine in the first step, and calcining at 550 ℃ for 3-5 h in a muffle furnace at a heating rate of 3-7 ℃/min.
In the second step, the block C is put into3N4After grinding, thermal oxidation is carried out for 1-3 h at a temperature rise rate of 3-7 ℃/min at 500 ℃.
Powder g-C in step III3N4The mass ratio of the L-ascorbic acid to the L-ascorbic acid is 1 (0.25-0.45), and the L-ascorbic acid are ground in an agate mortar for 20-40 min after being mixed; and transferring the mixed powder into a tube furnace, raising the temperature to 300 ℃ at a heating rate of 3-5 ℃/min under the nitrogen atmosphere, keeping the temperature for 2-4 h, and carrying out thermal reaction.
g-C in step four3N4The ratio of the copper powder to deionized water is 1g: 40-60 mL, ultrasonic treatment is carried out for 20-40 min, and Cu (NO) is added3)2·3H2O and g-C3N4The mass ratio of the NaOH solution to the water is 1 (1-3), stirring is carried out for 1-3 hours, and 8-12 mL of NaOH solution is dripped at the same time, wherein the concentration of the NaOH solution is 1 mol/L.
And fifthly, centrifuging the product at the rotating speed of more than 6000rpm for 20-40 min, and vacuum drying the solid-phase precipitate obtained by centrifuging at the temperature of 60-70 ℃ for more than 10 h.
And fifthly, heating the dried product to 250 ℃ at the speed of 4-6 ℃/min in a tubular furnace, and calcining for 2-3 h.
Compared with the prior art, the invention has the following advantages:
1. CuO/O-g-C prepared by the invention3N4The cathode material can bring excellent rate performance, cycle stability and capacity increase of the lithium ion battery. O-g-C3N4The porous structure of the electrolyte enables the CuO microspheres to be in full contact with the electrolyte, prevents the CuO microspheres from agglomerating, and promotes Li+Engaging and disengagingAnd accelerate charge transfer. Secondly, oxygen doping can increase g-C3N4Thereby improving the electrical conductivity of CuO/O-g-C3N4Electrical conductivity of the negative electrode.
2. Porous CuO/O-g-C3N4The cathode material can provide effective space to reduce structural damage caused by volume change and enhance the structural stability of the cathode material. The cathode material has the advantages of stable structure, difficult agglomeration, large specific surface area, good processing performance and the like, can obviously improve the contact area of the cathode material and electrolyte, increase electrode reaction sites, increase the transmission rate of lithium ions, and improve the coulombic efficiency and the multiplying power performance of the cathode material.
3. The oxygen doping and irreversible Cu nanoparticles of the present invention result in CuO/O-g-C3N4The charge transfer resistance of the negative electrode decreases. Oxygen doping strengthens CuO and O-g-C3N4The interaction between them, due to the presence of C-O-C and C-O bonds, ensures a stable structure during cycling.
4. The invention adopts a method for calcining g-C at low temperature3N4And L-ascorbic acid to synthesize oxygen-enriched doped g-C3N4A simple and effective way. The main products of L-ascorbic acid after thermal decomposition are furan derivatives and five-membered alpha, beta-unsaturated cyclic ketones, which can be used as oxygen doping source.
Drawings
FIG. 1 is a diagram of CuO/O-g-C prepared in example 1 of the present invention3N4Scanning electron micrographs of the material.
FIG. 2 is a diagram of CuO/O-g-C prepared in example 1 of the present invention3N4X-ray diffraction pattern of the material.
FIG. 3 is a view showing CuO/O-g-C prepared in example 1 of the present invention3N4The rate performance curve of the material.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: 9g of melamine was placed in a crucible with a lid and calcined in a muffle furnace at 550 ℃ for 4h at a rate of 5 ℃/min in air to obtain a block C3N4；
Step two: putting the block C3N4After fully grinding, carrying out thermal oxidation at 500 ℃ for 2h at the heating rate of 5 ℃/min to obtain powdery g-C3N4；
Step three: 2g of powder g-C3N4And 0.7g of L-ascorbic acid are ground in an agate mortar for 30min, then the mixed powder is transferred to a tubular furnace, the temperature is raised to 300 ℃ at the heating rate of 4 ℃/min under the nitrogen atmosphere, the thermal reaction is carried out at the constant temperature for 3h, after the reaction is finished, the sample is naturally cooled to the room temperature, and the O-g-C is ground in the agate mortar again to obtain the O-g-C3N4；
Step four: 1g of O-g-C3N4Dissolving in 50mL deionized water, ultrasonic treating for 30min, and adding 0.5g Cu (NO)3)2·3H2Stirring O for 2 hours, and dripping 10mL of NaOH (1mol/L) solution while stirring;
step five: collecting the product after stirring, centrifuging at 7000rpm for 30min until pH of colorless filtrate is neutral, vacuum drying the solid precipitate at 65 deg.C for 12h, heating to 250 deg.C at 5 deg.C/min in a tubular furnace, and calcining for 2.5h to obtain CuO/O-g-C3N4A lithium ion battery cathode material.
FIG. 1 is a schematic representation of CuO/O-g-C prepared in this example3N4Scanning electron micrographs of the material. It can be seen that the CuO microspheres are uniformly dispersed in g-C3N4In the matrix, CuO/O-g-C constituting a three-dimensional porous structure3N4And (3) a negative electrode material.
FIG. 2 is a diagram of CuO/O-g-C prepared in this example3N4X-ray diffraction pattern of the material. As can be seen, CuO/O-g-C3N4The peak formed at around 15 ℃ belongs to the group O-g-C3N4The (100) plane of the aromatic structure. CuO/O-g-C3N4Negative electrode materialThe XRD diffraction peak position of the material is consistent with that of CuO (PDF48-1548), which indicates that O-g-C3N4The coexistence structure of CuO and CuO shows that CuO is effectively attached to O-g-C3N4A surface.
FIG. 3 is a view showing CuO/O-g-C prepared in this example3N4The rate performance curve of the material. Circulating for 10 circles under different current densities, returning to 0.2 and 0.1A/g after the current densities are from 0.1, 0.2, 0.5, 1, 2 and 5A/g, and testing the circulation reversibility of the material, which can be seen from figure 3, CuO/O-g-C3N4The material shows excellent rate performance, particularly, the negative electrode material can be basically recovered to the initial charge-discharge capacity after being charged and discharged by large current and then being charged and discharged by small current, and CuO/O-g-C is displayed3N4The material has good cycle reversibility.
Example 2
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: placing 8g of melamine into a crucible with a cover, calcining at 550 ℃ for 5h in a muffle furnace at a heating rate of 3 ℃/min in the air atmosphere to obtain a block C3N4；
Step two: putting the block C3N4After fully grinding, carrying out thermal oxidation at a heating rate of 3 ℃/min at 500 ℃ for 3h to obtain powdery g-C3N4；
Step three: 2g of powder g-C3N4And 0.5g of L-ascorbic acid are ground in an agate mortar for 20min, then the mixed powder is transferred to a tubular furnace, the temperature is raised to 300 ℃ at the heating rate of 3 ℃/min under the nitrogen atmosphere, the thermal reaction is carried out for 4h at constant temperature, after the reaction is finished, the sample is naturally cooled to the room temperature, and the O-g-C is ground in the agate mortar again to obtain the O-g-C3N4；
Step four: 1g of O-g-C3N4Dissolving in 40mL deionized water, ultrasonic treating for 20min, and adding 0.4g Cu (NO)3)2·3H2Stirring O for 1h, and dropwise adding 8mL of NaOH (1mol/L) solution while stirring;
step five: stirring knotThen collecting the obtained product, centrifuging and washing at a centrifugal rotation speed of 7000rpm for 20min until the pH value of colorless filtrate reaches neutral, vacuum drying the solid-phase precipitate obtained by centrifuging at 60 ℃ for 12h, heating the dried product to 250 ℃ at a speed of 4 ℃/min in a tubular furnace, and calcining for 3h to obtain CuO/O-g-C3N4A lithium ion battery cathode material.
Example 3
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: 10g of melamine was placed in a crucible with a lid and calcined in a muffle furnace at 550 ℃ for 3h at a heating rate of 7 ℃/min in the air atmosphere to obtain a block C3N4；
Step two: putting the block C3N4After fully grinding, carrying out thermal oxidation at a heating rate of 7 ℃/min at 500 ℃ for 1h to obtain powdery g-C3N4；
Step three: 2g of powder g-C3N4And 0.9g of L-ascorbic acid are ground in an agate mortar for 40min, then the mixed powder is transferred to a tubular furnace, the temperature is raised to 300 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, the temperature is kept for 2h for thermal reaction, after the reaction is finished, the sample is naturally cooled to the room temperature, and the O-g-C is ground in the agate mortar again to obtain O-g-C3N4；
Step four: 1g of O-g-C3N4Dissolving in 60mL deionized water, ultrasonic treating for 40min, and adding 1g Cu (NO)3)2·3H2Stirring the mixture for 3 hours, and dropwise adding 12mL of NaOH (1mol/L) solution while stirring;
step five: collecting the product after stirring, centrifuging at 7000rpm for 40min until pH of colorless filtrate is neutral, vacuum drying the solid precipitate at 60 deg.C for 12h, heating to 250 deg.C at 6 deg.C/min in a tubular furnace, and calcining for 2h to obtain CuO/O-g-C3N4A lithium ion battery cathode material.
Example 4
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: 9g of melamine was placed in a crucible with a lid and calcined in a muffle furnace at 550 ℃ for 4h at a heating rate of 4 ℃/min in the air atmosphere to obtain a block C3N4；
Step two: putting the block C3N4After fully grinding, carrying out thermal oxidation at a temperature rise rate of 4 ℃/min at 500 ℃ for 3h to obtain powdery g-C3N4；
Step three: mixing 1g of powder g-C3N4And 0.25g of L-ascorbic acid are ground in an agate mortar for 20min, then the mixed powder is transferred to a tubular furnace, the temperature is raised to 300 ℃ at the heating rate of 4 ℃/min under the nitrogen atmosphere, the thermal reaction is carried out for 4h at constant temperature, after the reaction is finished, the sample is naturally cooled to the room temperature, and the O-g-C is ground in the agate mortar again to obtain the O-g-C3N4；
Step four: 0.5g of O-g-C3N4Dissolving in 25mL deionized water, ultrasonic treating for 20min, and adding 0.25g Cu (NO)3)2·3H2Stirring O for 1h, and dropwise adding 9mL of NaOH (1mol/L) solution while stirring;
step five: collecting the product after stirring, centrifuging at 7000rpm for 30min until pH of colorless filtrate is neutral, vacuum drying the solid precipitate at 60 deg.C for 12h, heating to 250 deg.C at 4 deg.C/min in a tubular furnace, and calcining for 2h to obtain CuO/O-g-C3N4A lithium ion battery cathode material.
Example 5
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: 10g of melamine was placed in a crucible with a lid and calcined in a muffle furnace at 550 ℃ for 4h at a heating rate of 6 ℃/min in the air atmosphere to obtain a block C3N4；
Step two: putting the block C3N4After fully grinding, the temperature is raised to 500 ℃ at a heating rate of 6 ℃/minThermal oxidizing for 1h to obtain powder g-C3N4；
Step three: mixing 3g of powder g-C3N4Grinding 1.35g of L-ascorbic acid in an agate mortar for 40min, transferring the mixed powder into a tubular furnace, heating to 300 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, keeping the temperature for 2h for thermal reaction, naturally cooling the sample to room temperature after the reaction is finished, and grinding in the agate mortar again to obtain O-g-C3N4；
Step four: 2g of O-g-C3N4Dissolving in 100mL deionized water, ultrasonic treating for 40min, and adding 2g Cu (NO)3)2·3H2Stirring the mixture for 3 hours, and dropwise adding 12mL of NaOH (1mol/L) solution while stirring;
step five: collecting the product after stirring, centrifuging at 7000rpm for 30min until pH of colorless filtrate is neutral, vacuum drying the solid precipitate at 60 deg.C for 12h, heating to 250 deg.C at 5 deg.C/min in a tubular furnace, and calcining for 3h to obtain CuO/O-g-C3N4A lithium ion battery cathode material.
Example 6
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: putting 8g of melamine into a crucible with a cover, calcining the melamine in a muffle furnace at 550 ℃ for 3h at a heating rate of 7 ℃/min in the air atmosphere to obtain a block C3N4；
Step two: putting the block C3N4After fully grinding, carrying out thermal oxidation at a heating rate of 3 ℃/min at 500 ℃ for 3h to obtain powdery g-C3N4；
Step three: 2g of powder g-C3N4And 0.7g of L-ascorbic acid are ground in an agate mortar for 30min, then the mixed powder is transferred to a tubular furnace, the temperature is raised to 300 ℃ at the heating rate of 4 ℃/min under the nitrogen atmosphere, the thermal reaction is carried out at the constant temperature for 3h, after the reaction is finished, the sample is naturally cooled to the room temperature, and the mixture is ground in the agate mortar againTo obtain O-g-C3N4；
Step four: 1g of O-g-C3N4Dissolving in 50mL deionized water, ultrasonic treating for 30min, and adding 0.5g Cu (NO)3)2·3H2Stirring O for 2 hours, and dripping 10mL of NaOH (1mol/L) solution while stirring;
step five: collecting the product after stirring, centrifuging at 7000rpm for 20min until pH of colorless filtrate is neutral, vacuum drying the solid precipitate at 60 deg.C for 12h, heating to 250 deg.C at 5 deg.C/min in a tubular furnace, and calcining for 2h to obtain CuO/O-g-C3N4A lithium ion battery cathode material.
Claims (8)
1. CuO/O-g-C3N4The lithium ion battery cathode material is characterized in that CuO/O-g-C3N4The lithium ion battery cathode material is of a three-dimensional heterostructure, and CuO microspheres are uniformly dispersed in g-C3N4In the matrix, g-C3N4The CuO microsphere has a large surface area and an adjustable porous layer structure, and the intrinsic energy band structure of the CuO microsphere is reduced by oxygen doping, so that the conductivity is improved, the CuO microsphere is in full contact with the electrolyte of a lithium ion battery, CuO agglomeration is prevented, and the volume expansion of CuO in the charging and discharging process is effectively inhibited.
2. A CuO/O-g-C as claimed in claim 13N4The preparation method of the lithium ion battery negative electrode material is characterized by comprising the following steps of:
the method comprises the following steps: putting melamine into a crucible with a cover, and calcining in a muffle furnace to obtain a block C3N4；
Step two: the obtained block C3N4Fully grinding the mixture and then carrying out thermal oxidation to obtain powdery g-C3N4；
Step three: the obtained powder g-C3N4And L-ascorbic acid in an agate mortar, and transferring the mixed powder to a tubeIn a furnace, carrying out thermal reaction in nitrogen atmosphere, naturally cooling the sample to room temperature after the reaction is finished, and grinding in an agate mortar again to obtain O-g-C3N4；
Step four: mixing O-g-C3N4Dissolving in deionized water, ultrasonic treating, and adding Cu (NO)3)2·3H2Stirring O, and dripping NaOH solution while stirring;
step five: after stirring, collecting the obtained product, carrying out centrifugal washing until the pH value of colorless filtrate reaches neutral, carrying out vacuum drying treatment, and carrying out heat treatment on the dried product to obtain CuO/O-g-C3N4A lithium ion battery cathode material.
3. A CuO/O-g-C according to claim 23N4The preparation method of the lithium ion battery cathode material is characterized in that 8-10 g of melamine is added in the step one, and the mixture is calcined in a muffle furnace at 550 ℃ for 3-5 h at the heating rate of 3-7 ℃/min.
4. A CuO/O-g-C according to claim 23N4The preparation method of the lithium ion battery cathode material is characterized in that the blocky C is subjected to the step two3N4After grinding, thermal oxidation is carried out for 1-3 h at a temperature rise rate of 3-7 ℃/min at 500 ℃.
5. A CuO/O-g-C according to claim 23N4The preparation method of the lithium ion battery cathode material is characterized in that the powder g-C is prepared in the third step3N4The mass ratio of the L-ascorbic acid to the L-ascorbic acid is 1 (0.25-0.45), and the L-ascorbic acid are ground in an agate mortar for 20-40 min after being mixed; and transferring the mixed powder into a tube furnace, raising the temperature to 300 ℃ at a heating rate of 3-5 ℃/min under the nitrogen atmosphere, keeping the temperature for 2-4 h, and carrying out thermal reaction.
6. A CuO/O-g-C according to claim 23N4The preparation method of the lithium ion battery cathode material is characterized by comprising the fourth stepThe O-g-C3N4The ratio of the copper powder to deionized water is 1g: 40-60 mL, ultrasonic treatment is carried out for 20-40 min, and Cu (NO) is added3)2·3H2O and O-g-C3N4The mass ratio of the NaOH solution to the water is 1 (1-3), stirring is carried out for 1-3 hours, and 8-12 mL of NaOH solution is dripped at the same time, wherein the concentration of the NaOH solution is 1 mol/L.
7. A CuO/O-g-C according to claim 23N4The preparation method of the lithium ion battery cathode material is characterized in that the rotating speed of the product subjected to centrifugation in the fifth step is more than 6000rpm, the centrifugation time is 20-40 min, and the solid-phase precipitate obtained through centrifugation is dried for more than 10 hours in vacuum at the temperature of 60-70 ℃.
8. A CuO/O-g-C according to claim 23N4The preparation method of the lithium ion battery cathode material is characterized in that the product dried in the fifth step is calcined in a tubular furnace for 2-3 hours at the temperature rising to 250 ℃ at the speed of 4-6 ℃/min.
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