CN113019455A - Copper-doped nitrogen-enriched cobalt phthalocyanine nano material, preparation method thereof and application of copper-doped nitrogen-enriched cobalt phthalocyanine nano material as lithium thionyl chloride battery anode catalyst - Google Patents
Copper-doped nitrogen-enriched cobalt phthalocyanine nano material, preparation method thereof and application of copper-doped nitrogen-enriched cobalt phthalocyanine nano material as lithium thionyl chloride battery anode catalyst Download PDFInfo
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- CN113019455A CN113019455A CN202110256506.9A CN202110256506A CN113019455A CN 113019455 A CN113019455 A CN 113019455A CN 202110256506 A CN202110256506 A CN 202110256506A CN 113019455 A CN113019455 A CN 113019455A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 154
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 80
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 23
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910006124 SOCl2 Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 24
- 239000013590 bulk material Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 230000002093 peripheral effect Effects 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract description 13
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- -1 tetrapropylphenyl Chemical group 0.000 description 1
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Abstract
The invention discloses a copper-doped nitrogen-enriched cobalt phthalocyanine nano material, a preparation method thereof and application of the copper-doped nitrogen-enriched cobalt phthalocyanine nano material as a lithium thionyl chloride battery anode catalyst, wherein the method comprises the steps of firstly synthesizing a copper-doped nitrogen-enriched cobalt phthalocyanine block by using an in-situ solid phase method, then dissolving the copper-doped nitrogen-enriched cobalt phthalocyanine block by using concentrated sulfuric acid,in an ultrasonic environment, the copper-doped nitrogen-enriched cobalt phthalocyanine is quickly nucleated to synthesize the copper-doped nitrogen-enriched cobalt phthalocyanine nano material. The method has the characteristics of simple operation, short period, low energy consumption, good repeatability, high yield and the like. The copper-doped nitrogen-enriched cobalt phthalocyanine nano material prepared by the in-situ solid phase method is used as Li/SOCl2The positive electrode catalyst (2) can be used to make the discharge time of the battery long and 38 minutes (the current density is 40 mA/cm)2) High voltage platform and large actual output specific energy, and can be used as Li/SOCl2The battery is a good anode catalytic material.
Description
Technical Field
The invention belongs to Li/SOCl2The technical field of preparation of battery anode catalytic materials, in particular to a method for preparing Li/SOCl by using an in-situ solid phase method2A preparation method and application of a catalytic material copper doped nitrogen-enriched cobalt phthalocyanine for a battery anode.
Background
The lithium thionyl chloride battery is a primary inorganic non-aqueous electrolyte battery having a stable voltage plateau, a wide range of use temperatures, a long storage life and no heavy metal elements. [ Y.O.Ko, C.T.Lee, Effects of the structural characteristics of carbon cathode on the initial voltage delay in Li/SOCl2 battery,J.Ind.Eng.Chem.18(2012)726-730.]Commercial applications are currently divided into both capacity and power type batteries. The capacity type battery is mainly applied to various intelligent meters, memories, backup power supplies, remote monitoring systems and emerging shared bicycles. The power type battery is mainly applied to aviation, aerospace, navigation electronics and water, land and air weapons. Li, Z.Z.Yuan, Y.Xu, J.C.Liu, Co-N-macroporous modified graphene with an extracellular electrolytic activity for lithium-cellulose, Electrochim.acta 217(2016)73-79.]According to the formula P, UI and U2and/R, the battery is under constant resistance (namely the same equipment), and the improvement of the voltage platform is beneficial to the improvement of the output power of the battery. At present, three ways for improving a battery voltage platform are basically provided, the first way is to add a swelling agent such as ammonium bicarbonate on the positive carbon to improve the mesoporous rate of the positive carbon. The second is to add PVC powder, Li, to the electrolyte2B10Cl10And MnO2And the like, to improve the conductivity of the passivation film. The third method is to add catalyst such as carbon nanotube, graphene, pyridine and metal phthalocyanine into electrolyte to increase SOCl2The reduction rate of (c). However, the addition of a catalyst to the electrolyte can block the pores of the carbon anode, affecting the sustained discharge of the cell. An improved method is to fix the catalyst directly inside the porous carbon, and the choice of a suitable catalytic material becomes crucial.
The metal phthalocyanine and the derivative thereof structurally present a closed continuous 18 pi electron conjugated system, are good electron donors and have excellent catalytic activity. When the metal phthalocyanine is used as a lithium thionyl chloride battery anode catalytic material, the discharge time and the voltage plateau of the battery are remarkably improved. The N-doped phthalocyanine has a similar structure to phthalocyanine, also has an 18 pi electron conjugated system and strong aromaticity, and is also a good electron donor and electron acceptor. Bulk N-doped metal phthalocyanines (M ═ Mn)2+,Ni2+,Fe2+,Co2+) When the catalyst is added into electrolyte to be used as the anode catalyst of the lithium thionyl chloride battery, the actual specific energy is improved by about 60-120 percent. [ K.Li, Z.W.Xu, X.T.Shen, K.Yao, J.S.ZHao, R.L.ZHang, J.ZHang, L.Wang, and J.F.Zhu.cobalt tetrapropylphenyl azine nanoparticles and carbon nanotubes for long-voltage Li/SOCl2 batteries Electrochim.Acta,2019,295,569-576.]。
So far, copper-doped nitrogen-enriched cobalt phthalocyanine has not been reported, and the copper-doped nitrogen-enriched cobalt phthalocyanine has a remarkable improvement on the discharge voltage of a battery when being used as a lithium thionyl chloride positive electrode catalyst.
Disclosure of Invention
The invention aims to provide a copper-doped nitrogen-rich cobalt phthalocyanine nano material, a preparation method thereof and application of the copper-doped nitrogen-rich cobalt phthalocyanine nano material as a lithium thionyl chloride battery anode catalyst2The battery anode catalytic material has the advantages of long discharge time of the battery, high voltage plateau and actual output ratioLarge energy and the like.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a copper-doped nitrogen-enriched cobalt phthalocyanine nano material, which comprises the following steps:
1) mixing 2, 3-pyridinedicarboxylic acid, urea and CoCl2·6H2O、CuCl2·2H2O and (NH)4)6Mo7O24·4H2O, fully mixing and uniformly grinding to obtain a mixture;
2) carrying out heat treatment on the mixture in the air atmosphere, and then cleaning and drying a product obtained by the heat treatment to obtain a copper-doped nitrogen-enriched cobalt phthalocyanine bulk material;
3) dissolving copper-doped nitrogen-enriched cobalt phthalocyanine bulk material in concentrated sulfuric acid, and uniformly stirring until the copper-doped nitrogen-enriched cobalt phthalocyanine bulk material is completely dissolved;
4) and (3) pouring the product obtained in the step 3) into water for treatment for 30-180 s under an ultrasonic condition, and then performing suction filtration, cleaning and drying to obtain the copper-doped nitrogen-enriched cobalt phthalocyanine nano material.
Preferably, in step 1), 2, 3-pyridinedicarboxylic acid, urea, CoCl2·6H2O、CuCl2·2H2O and (NH)4)6Mo7O24·4H2The mass ratio of O is (5-10): (10-15): (4-8): (0.5-1.5): (0.8-2).
Preferably, in step 2), the heat treatment is performed by placing the mixture in a crucible and performing heat treatment in a muffle furnace, and specifically, the operations are as follows: raising the temperature of the mixture from room temperature to 100-180 ℃ at a temperature rise speed of 5-15 ℃/min, preserving heat for 0.5-1.5 h, then heating to 200-400 ℃ at a temperature rise speed of 5-15 ℃/min, preserving heat for 1-4 h, and cooling to room temperature.
Preferably, in the step 3), the ratio of (0.1-1) g: (5-50) mL, and dissolving the copper-doped nitrogen-enriched cobalt phthalocyanine bulk material in concentrated sulfuric acid.
Preferably, in the step 4), the ultrasonic condition is 10-50 KHz.
The invention also discloses the copper-doped nitrogen-enriched cobalt phthalocyanine material prepared by the preparation method, and the copper-doped nitrogen-enriched cobalt phthalocyanine material contains peripheral active site pyridine N and Cu and Co double metal ions.
The invention also discloses the application of the copper-doped nitrogen-enriched cobalt phthalocyanine nano material as Li/SOCl2Application of battery anode catalyst.
Preferably, the copper-doped nitrogen-enriched cobalt phthalocyanine nano material is used as Li/SOCl2When the battery anode catalyst is used, the discharge time of the battery reaches 38 minutes, and the current density is 40mA/cm2。
Compared with the prior art, the invention has the following beneficial effects:
the method for preparing the copper-doped nitrogen-enriched cobalt phthalocyanine nano material disclosed by the invention is novel in design, and a copper-doped nitrogen-enriched cobalt phthalocyanine block is firstly synthesized by utilizing an in-situ solid phase method, wherein the arrangement sequence of copper phthalocyanine is different from that of cobalt phthalocyanine, and the copper is doped in the cobalt phthalocyanine, so that the reactive sites are favorably improved. Meanwhile, the potential of copper is favorable for accelerating SOCl by cobalt ions2The reduction rate of (c). And then dissolving the copper-doped nitrogen-enriched cobalt phthalocyanine block by using concentrated sulfuric acid, and quickly nucleating the copper-doped nitrogen-enriched cobalt phthalocyanine block in an ultrasonic environment to synthesize the copper-doped nitrogen-enriched cobalt phthalocyanine nano material. The nanomaterial is advantageous in increasing its reaction area by increasing the specific surface area. The copper-doped nitrogen-enriched cobalt phthalocyanine nano material on the molecular level has a peripheral active site pyridine N and Cu and Co double metal ions, and can improve Li/SOCl2Discharge time of the battery, voltage plateau and actual output specific energy. The method has the characteristics of simple operation, short period, low energy consumption, good repeatability, high yield and the like.
The copper-doped nitrogen-enriched cobalt phthalocyanine nano material prepared by the in-situ solid phase method is used as Li/SOCl2The positive electrode catalyst (2) has a long discharge time of 38 minutes (about 26 minutes in general, about 30 minutes in general, for a normal cell without a catalyst), and a current density of 40mA/cm2High voltage platform and large actual output specific energy, and can be used as Li/SOCl2The battery is a good anode catalytic material.
Drawings
FIG. 1 is an XRD pattern of copper doped cobalt phthalocyanine (Co/CuTAP) prepared in example 1 of the present invention;
FIG. 2 is an electron micrograph of Co/CuTAP prepared in example 3 of the present invention; wherein (a) is an SEM picture of Co/CuTAP; (b) TEM image of Co/CuTAP;
FIG. 3 shows Li/SOCl of Co/CuTAP obtained in example 52Discharge profile of the battery.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
A method for preparing a copper-doped nitrogen-enriched cobalt phthalocyanine nano material by an in-situ solid phase method comprises the following steps:
1) 5g of 2, 3-pyridinedicarboxylic acid, 10g of urea, 4g of CoCl2·6H2O、0.5g CuCl2·2H2O and 0.8g (NH)4)6Mo7O24·4H2O, fully mixing and uniformly grinding to obtain a mixture;
2) and putting the prepared mixture into a muffle furnace in an air atmosphere, raising the temperature of the mixture from room temperature to 100 ℃ at a temperature rise speed of 5 ℃/min, preserving the heat for 0.5h, then heating to 200 ℃ at a temperature rise speed of 5 ℃/min, preserving the heat for 1h, and cooling to room temperature. Finally, cleaning and drying a product obtained by heat treatment to prepare a copper-doped nitrogen-enriched cobalt phthalocyanine bulk material;
3) dissolving 0.1g of copper-doped nitrogen-enriched cobalt phthalocyanine bulk material in 5ml of concentrated sulfuric acid, and uniformly stirring until the copper-doped nitrogen-enriched cobalt phthalocyanine bulk material is completely dissolved;
4) and (3) putting 1000ml of deionized water into a beaker, pouring the product obtained in the step (3) into the beaker under the environment of 10KHz ultrasound for 30s, and then carrying out suction filtration, cleaning and drying to obtain the copper-doped nitrogen-enriched cobalt phthalocyanine nano material.
Referring to fig. 1, the resulting product is Co/CuTAP as can be taken from fig. 1, and by comparing the product XRD patterns, it shows that the presence of Co/CuTAP nanomaterials is demonstrated at 7.00, 23.27, 17.10 and 27.29 °.
Example 2
A method for preparing a copper-doped nitrogen-enriched cobalt phthalocyanine nano material by an in-situ solid phase method comprises the following steps:
1) 6g of 2, 3-pyridinedicarboxylic acid, 12g of urea, 7g of CoCl2·6H2O、0.7g CuCl2·2H2O and 1.2g (NH)4)6Mo7O24·4H2O, fully mixing and uniformly grinding to obtain a mixture;
2) and (2) putting the prepared mixture into a muffle furnace in an air atmosphere, raising the temperature of the mixture from room temperature to 180 ℃ at a temperature rise speed of 5-15 ℃/min, preserving the heat for 1.5h, heating to 400 ℃ at a temperature rise speed of 15 ℃/min, preserving the heat for 4h, and cooling to room temperature. Finally, cleaning and drying the product obtained by the heat treatment to prepare a copper-doped nitrogen-enriched cobalt phthalocyanine bulk material;
3) 1g of copper-doped nitrogen-enriched cobalt phthalocyanine bulk material is dissolved in 50ml of concentrated sulfuric acid, and the mixture is uniformly stirred until the copper-doped nitrogen-enriched cobalt phthalocyanine bulk material is completely dissolved;
4) and (3) putting 5000ml of deionized water into a beaker, pouring the product obtained in the step (3) into the beaker under the environment of 50KHz ultrasound for 180s, and then carrying out suction filtration, cleaning and drying to obtain the copper-doped nitrogen-enriched cobalt phthalocyanine nano material.
Example 3
A method for preparing a copper-doped nitrogen-enriched cobalt phthalocyanine nano material by an in-situ solid phase method comprises the following steps:
1) 8g of 2, 3-pyridinedicarboxylic acid, 15g of urea, 7g of CoCl2·6H2O、1.3g CuCl2·2H2O and 1.5g (NH)4)6Mo7O24·4H2O, fully mixing and uniformly grinding to obtain a mixture;
2) and putting the prepared mixture into a muffle furnace in an air atmosphere, raising the temperature of the mixture from room temperature to 150 ℃ at a heating rate of 10 ℃/min, preserving the heat for 1h, heating to 300 ℃ at a heating rate of 10 ℃/min, preserving the heat for 2h, and cooling to room temperature. Finally, cleaning and drying a product obtained by heat treatment to prepare a copper-doped nitrogen-enriched cobalt phthalocyanine bulk material;
3) dissolving 0.5g of copper-doped nitrogen-enriched cobalt phthalocyanine bulk material in 20ml of concentrated sulfuric acid, and uniformly stirring until the copper-doped nitrogen-enriched cobalt phthalocyanine bulk material is completely dissolved;
4) and (3) putting 2000ml of deionized water into a beaker, pouring the product obtained in the step (3) into the beaker under the environment of 20KHz ultrasound for 60s, and then carrying out suction filtration, cleaning and drying to obtain the copper-doped nitrogen-enriched cobalt phthalocyanine nano material.
Referring to fig. 2, wherein (a) SEM image of Co/cupap nanomaterial has a particle size width of about 50 nm; and (b) is a TEM image of the Co/CuTAP nanometer material, and metal ions at the upper bright spots can be seen.
Example 4
A method for preparing a copper-doped nitrogen-enriched cobalt phthalocyanine nano material by an in-situ solid phase method comprises the following steps:
1) 8g of 2, 3-pyridinedicarboxylic acid, 10g of urea, 6g of CoCl2·6H2O、1g CuCl2·2H2O and 2g (NH)4)6Mo7O24·4H2O, fully mixing and uniformly grinding to obtain a mixture;
2) and putting the prepared mixture into a muffle furnace in an air atmosphere, raising the temperature of the mixture from room temperature to 160 ℃ at a temperature rise speed of 5 ℃/min, preserving the heat for 0.5h, then heating to 300 ℃ at a temperature rise speed of 10 ℃/min, preserving the heat for 2h, and cooling to room temperature. Finally, cleaning and drying a product obtained by heat treatment to prepare a copper-doped nitrogen-enriched cobalt phthalocyanine bulk material;
3) dissolving 0.5g of copper-doped nitrogen-enriched cobalt phthalocyanine bulk material in 25ml of concentrated sulfuric acid, and uniformly stirring until the copper-doped nitrogen-enriched cobalt phthalocyanine bulk material is completely dissolved;
4) and (3) placing 2500ml of deionized water into a beaker, pouring the product obtained in the step (3) into the beaker under the environment of 50KHz ultrasound for 120s, and then carrying out suction filtration, cleaning and drying to obtain the copper-doped nitrogen-enriched cobalt phthalocyanine nano material.
Example 5
A method for preparing a copper-doped nitrogen-enriched cobalt phthalocyanine nano material by an in-situ solid phase method comprises the following steps:
1) 7g of 2, 3-pyridinedicarboxylic acid, 11g of urea, 4g of CoCl2·6H2O、0.5g CuCl2·2H2O and 0.8g (NH)4)6Mo7O24·4H2O, fully mixing and uniformly grinding to obtain a mixture;
2) and putting the prepared mixture into a muffle furnace in an air atmosphere, raising the temperature of the mixture from room temperature to 120 ℃ at a temperature rise speed of 5 ℃/min, preserving the heat for 0.5h, then heating to 320 ℃ at a temperature rise speed of 15 ℃/min, preserving the heat for 2h, and cooling to room temperature. Finally, cleaning and drying a product obtained by heat treatment to prepare a copper-doped nitrogen-enriched cobalt phthalocyanine bulk material;
3) dissolving 0.6g of copper-doped nitrogen-enriched cobalt phthalocyanine bulk material in 30ml of concentrated sulfuric acid, and uniformly stirring until the copper-doped nitrogen-enriched cobalt phthalocyanine bulk material is completely dissolved;
4) and (3) putting 5000ml of deionized water into a beaker, pouring the product obtained in the step (3) into the beaker under the environment of 30KHz ultrasound for 30s, and then carrying out suction filtration, cleaning and drying to obtain the copper-doped nitrogen-enriched cobalt phthalocyanine nano material.
Referring to fig. 3, it can be seen from fig. 3 that the Li/SOCl2 battery with the Co/cupap nanomaterial added has a discharge time as long as 38 minutes. The electrochemical performance of the Li/SOCl2 battery is obviously improved after the anode catalytic material Co/CuTAP nanometer material is added.
In summary, the invention discloses a method for preparing copper-doped nitrogen-enriched cobalt phthalocyanine nano material by an in-situ solid phase method, the design concept is novel, the method utilizes the in-situ solid phase method to firstly synthesize copper-doped nitrogen-enriched cobalt phthalocyanine blocks, the copper phthalocyanine is different from the cobalt phthalocyanine in the row sequence, and the copper is doped in the cobalt phthalocyanine, thereby being beneficial to improving the reactive sites. Meanwhile, the potential of copper is favorable for accelerating SOCl by cobalt ions2The reduction rate of (c). And then dissolving the copper-doped nitrogen-enriched cobalt phthalocyanine block by using concentrated sulfuric acid, and quickly nucleating the copper-doped nitrogen-enriched cobalt phthalocyanine block in an ultrasonic environment to synthesize the copper-doped nitrogen-enriched cobalt phthalocyanine nano material. The nanomaterial is beneficial to increasing the reaction area of the nanomaterial by increasing the specific surface area. The copper-doped nitrogen-enriched cobalt phthalocyanine nano material on the molecular level has a peripheral active site pyridine N and also has Cu and Co double metal ions, and can improve Li/SOCl2Discharge time of the battery, voltage plateau and actual specific output energy. The method has the characteristics of simple operation, short period, low energy consumption, good repeatability, high yield and the like. The copper-doped nitrogen-enriched cobalt phthalocyanine nano material prepared by the in-situ solid phase method is used as Li/SOCl2The positive electrode catalyst (2) can provide a battery having a long discharge time of 38 minutes (current density of 40 mA/cm)2) High voltage platform and large practical output specific energy, and can be used as Li/SOCl2The battery is a good anode catalytic material.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.
Claims (8)
1. A preparation method of a copper-doped nitrogen-enriched cobalt phthalocyanine is characterized by comprising the following steps:
1) mixing 2, 3-pyridinedicarboxylic acid, urea and CoCl2·6H2O、CuCl2·2H2O and (NH)4)6Mo7O24·4H2O, fully mixing and uniformly grinding to obtain a mixture;
2) carrying out heat treatment on the mixture in the air atmosphere, and then cleaning and drying a product obtained by the heat treatment to obtain a copper-doped nitrogen-enriched cobalt phthalocyanine bulk material;
3) dissolving copper-doped nitrogen-enriched cobalt phthalocyanine bulk material in concentrated sulfuric acid, and uniformly stirring until the copper-doped nitrogen-enriched cobalt phthalocyanine bulk material is completely dissolved;
4) and (3) pouring the product obtained in the step 3) into water for treatment for 30-180 s under an ultrasonic condition, and then performing suction filtration, cleaning and drying to obtain the copper-doped nitrogen-enriched cobalt phthalocyanine nano material.
2. The method for preparing the copper-doped nitrogen-enriched cobalt phthalocyanine material according to claim 1, wherein in the step 1), 2, 3-pyridinedicarboxylic acid, urea and CoCl are adopted2·6H2O、CuCl2·2H2O and (NH)4)6Mo7O24·4H2The mass ratio of O is (5-10): (10-15): (4-8): (0.5-1.5): (0.8-2).
3. The method for preparing the copper-doped nitrogen-enriched cobalt phthalocyanine material according to claim 1, wherein in the step 2), the heat treatment is performed by placing the mixture in a crucible and performing heat treatment in a muffle furnace, and the method comprises the following specific operations: raising the temperature of the mixture from room temperature to 100-180 ℃ at a temperature rise speed of 5-15 ℃/min, preserving heat for 0.5-1.5 h, then heating to 200-400 ℃ at a temperature rise speed of 5-15 ℃/min, preserving heat for 1-4 h, and cooling to room temperature.
4. The method for preparing the copper-doped nitrogen-enriched cobalt phthalocyanine according to claim 1, wherein in the step 3), the ratio of (0.1-1) g: (5-50) mL, and dissolving the copper-doped nitrogen-enriched cobalt phthalocyanine bulk material in concentrated sulfuric acid.
5. The preparation method of the copper-doped nitrogen-enriched cobalt phthalocyanine according to claim 1, wherein in the step 4), the ultrasonic condition is 10-50 KHz.
6. The copper-doped nitrogen-enriched cobalt phthalocyanine nano material prepared by the preparation method of any one of claims 1-5 is characterized by comprising peripheral active site pyridine N and Cu and Co bimetallic ions.
7. The copper-doped cobalt phthalocyanine-rich nanomaterial of claim 6 as a Li/SOCl2Application of battery anode catalyst.
8. Use according to claim 7, wherein copper-doped cobalt phthalocyanine rich in nitrogen is used as Li/SOCl nanomaterial2When the battery anode catalyst is used, the discharge time of the battery reaches 38 minutes, and the current density is 40mA/cm2。
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