CN112968161A - Tetrapyridoporphyrin nickel/active carbon Li/SOCl2Battery carbon anode catalytic material and preparation method thereof - Google Patents
Tetrapyridoporphyrin nickel/active carbon Li/SOCl2Battery carbon anode catalytic material and preparation method thereof Download PDFInfo
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- CN112968161A CN112968161A CN202110138150.9A CN202110138150A CN112968161A CN 112968161 A CN112968161 A CN 112968161A CN 202110138150 A CN202110138150 A CN 202110138150A CN 112968161 A CN112968161 A CN 112968161A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Abstract
The invention discloses a tetrapyridoporphyrin nickel/active carbon Li/SOCl2The battery carbon anode catalytic material and the preparation method thereof specifically comprise 1) the following components in percentage by mass (0.92-2.12): (1.55-3.15): (0.68-1.48): (0.19-0.59): (0.10-0.30) weighing 2, 3-pyridinedicarboxylic acid, urea, nickel chloride hexahydrate, ammonium molybdate tetrahydrate and asphalt coke activated carbon, mixing and fully grinding uniformly to obtain a mixture; 2) sintering the mixture at 120-300 ℃ in an air atmosphere, and cooling to room temperature to obtain a crude product; 3) grinding the crude product, purifying and drying to obtain the nickel tetrapyridoporphyrin/active carbon Li/SOCl2A battery positive electrode catalytic material. The methodAsphalt coke Activated Carbon (AC) was used as a matrix to induce NiTAP nanocrystallization, fully expose active sites and improve conductivity. The tetrapyridoporphyrin nickel/active carbon Li/SOCl prepared by the method2The battery anode catalytic material has the advantages of prolonging the discharge time of the battery and improving the discharge voltage platform.
Description
Technical Field
The invention relates to the technical field of lithium primary batteries, in particular to nickel tetrapyridoporphyrin/active carbon Li/SOCl2A battery carbon anode catalytic material and a preparation method thereof.
Background
Lithium/thionyl chloride (Li/SOCl)2) The battery has the advantages of high specific energy (590W h/Kg), high working voltage (up to 3.6V), wide use temperature range (-55C-150C), long storage life (more than 10 years), no maintenance, low annual self-discharge rate (less than or equal to 1 percent) and the like, and is widely applied to military and civil fields such as aerospace, oil exploitation, medical equipment, intelligent electric meters, electronic cigarettes and the like at present. ([1]Du C,Liu S,Zhang W,et al.Nitrogen-Doped Carbon Nanotubes Based on Ionic Liquid Precursors as Effective Cathode Catalysts for Li/SOCl2Batteries[J].Journal of The Electrochemical Society,2018,165(9):A1955-A1960.[2]Gao Y,Li S,Wang X,et al.Carbon nanotubes chemically modified by metal phthalocyanines with excellent electrocatalytic activity to Li/SOCl2 battery[J].Journal of The Electrochemical Society,2017,164(6):A1140-A1147.)
Li/SOCl2In the battery, the negative electrode is lithium metal, and the positive active material is SOCl2Carbon as SOCl2The electrolyte is LiAlCl4-SOCl2And (3) solution. During the discharge process, on the one hand, the positive electrode SOCl2On the other hand, lithium ions in the negative electrode migrate to the surface of the carbon positive electrode to form a layer of lithium chloride film to hinder SOCl2The reduction reaction of (2) is further progressed, and finally the reaction is terminated without discharging electricity. ([3]Zhang R,Wang R,Luo K,et al.Multi-walled carbon nanotubes chemically modified by cobalt tetraaminophthalocyanines with excellent electrocatalytic activity to Li/SOCl2 battery[J].Journal of The Electrochemical Society,2014,161(14):H941-H949.[4]Gao Y,Chen L,Quan M,et al.A series of new Phthalocyanine derivatives with large conjugated system as catalysts for the Li/SOCl2 battery[J].Journal of Electroanalytical Chemistry,2018,808:8-13.)
Wherein, the tetrapyridoporphyrin complex (MTAP) has a macrocyclic conjugated system of 18 pi electrons and excellent acid and alkali stability, and the high electrocatalytic performance of MTAP is favorable for accelerating SOCl2Can be used as a catalytic material for Li/SOCl2A battery. Wherein MTAP and SOCl2The reaction between them is a surface coordination catalytic reaction, and the active site is located at the central metal ion and ligand of MTAP. The choice of central metal and ligand depends strongly on the catalytic activity and whether the active sites are sufficiently exposed. Ni in NiTAP2+Has an electronic configuration of 3d8Is easy to react with SOCl2The O atom forms an octahedral complex, which is favorable for catalyzing SOCl2And (3) reduction reaction of (2). Therefore, the catalytic activity is closely related to whether or not the active sites are sufficiently exposed. Generally, the synthesized MTAP is large in size and massive, active sites cannot be fully exposed, and the surface coordination catalytic reaction is not favorably carried out. By reducing the size of the MTAP to the nanoscale, the specific surface area is increased to expose more active sites, making the reaction more complete. Meanwhile, the conductivity of MTAP is low, so that the catalytic performance of MTAP is limited. ([5]Liu Z,Jiang Q,Zhang R,et al.Graphene/phthalocyanine composites andbinuclear metal phthalocyanines with excellentelectrocatalytic performance to Li/SOCl2 battery[J].ElectrochimicaActa,2016,187:81-91.[6]Xu Z,Li K,Hu H,etal.Frombulk to nano metal phthalocyanine by recrystallization with enhanced nucleation[J].Dyes and Pigments,2017,139:97-101.)
The carbon material has high conductivity, and MTAP is supported on a carbon substrate to improve the conductivity, and further, the structure can be effectively improved, and the structural stability can be maintained for a long time. More exposure as induced MTAP nanocrystallization with carbon nanotube loadingActive sites and improved conductivity. ([7]Xu Z,Li H,Cao G,et al.Electrochemical performance of carbon nanotube-supported cobalt phthalocyanine and its nitrogen-rich derivatives for oxygen reduction[J]Journal of Molecular Catalysis A: Chemical,2011,335(1-2):89-96.) however, carbon nanotubes or graphene tend to block the pores of acetylene black or entangle the acetylene black, thereby affecting Li/SOCl2The battery discharge time.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the nickel tetrapyridoporphyrin/active carbon Li/SOCl which has the advantages of excellent catalytic performance, safety, simple preparation, short period, high repeatability, lower cost and environmental protection2Preparation method of battery carbon anode catalytic material, and tetrapyridoporphyrin nickel/active carbon Li/SOCl prepared by method2The carbon anode catalytic material of the battery has the advantages of long battery discharge time and high and stable discharge voltage platform.
In order to achieve the purpose, the invention adopts the technical scheme that:
tetrapyridoporphyrin nickel/active carbon Li/SOCl2The preparation method of the battery carbon anode catalytic material is characterized in that; the method specifically comprises the following steps:
step 1: according to the mass ratio (0.92-2.12): (1.55-3.15): (0.68-1.48): (0.19-0.59): (0.10-0.30) weighing 2, 3-pyridinedicarboxylic acid, urea, nickel chloride hexahydrate, ammonium molybdate tetrahydrate and asphalt coke activated carbon, mixing and fully grinding uniformly to obtain a mixture;
step 2: in an air atmosphere, heating the mixture from room temperature to 120-160 ℃ at a heating rate of 4-10 ℃/min, then preserving heat for 0.3-1 h, then heating to 220-300 ℃ at a heating rate of 4-10 ℃/min, preserving heat for 0.5-3 h, and cooling to room temperature to obtain a crude product;
and step 3: grinding the crude product, washing and drying to obtain the nickel tetrapyridoporphyrin/active carbon Li/SOCl2A battery positive electrode catalytic material.
Further, the specific surface area of the pitch coke activated carbon in the step 1 is 1400m2/g。
Further, the washing process in the step 3 is to wash the mixture for multiple times by using deionized water and then sequentially filter the mixture by using deionized water and absolute ethyl alcohol.
Further, the drying in the step 3 is vacuum drying at 70 ℃ for 10-28 h.
Tetrapyridoporphyrin nickel/active carbon Li/SOCl prepared by adopting preparation method2The battery anode catalytic material is a porous structure formed by NiTAP in-situ growth on an AC surface, and the porous structure is uniform in size and distribution.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, asphalt coke Activated Carbon (AC) is used as a matrix, and the large specific surface area and high conductivity of the AC are utilized, and the surface contains rich functional groups such as carboxyl, carbonyl and the like, NiTAP is induced to be grown on the AC in a nanocrystallization manner, so that the stability of a catalytic material is improved, the size of MTAP is reduced to a nanometer level, active sites are fully exposed, the reaction is more thorough, and the conductivity is improved; MTAP and SOCl2In a surface coordination catalytic reaction of Ni2+Has an electronic configuration of 3d8Is easy to react with SOCl2The O atom forms an octahedral complex, which is favorable for catalyzing SOCl2Reduction reaction of (3); the morphology and the structure of the asphalt coke active carbon AC are matched with those of the acetylene black, so that the occurrence of hole plugging or winding is avoided.
2) The method adopts an in-situ solid phase method to synthesize the nickel tetrapyridoporphyrin/activated carbon composite material, has the advantages of simple and efficient synthesis process, short period, environmental protection, safety and the like, and is beneficial to industrial production.
3) The tetrapyridoporphyrin nickel/active carbon Li/SOCl prepared by the invention2The battery anode catalytic material is a porous structure with NiTAP in-situ grown on the AC surface, the size of the porous structure is consistent, the porous structure is uniformly distributed, and the accumulation of NiTAP is effectively prevented. The synergistic effect of NiTAP and AC is favorable to charge transport, so that the Li/SOCl pair of NiTAP/AC is improved2Catalytic activity of the cell.
Drawings
FIG. 1 shows the preparation of nickel tetrapyridoporphyrin/active carbon Li/SOCl2Catalytic material for battery positive electrode IAn R map;
FIG. 2 shows the preparation of nickel tetrapyridoporphyrin/active carbon Li/SOCl2SEM image of the battery positive electrode catalytic material;
FIG. 3 shows the preparation of nickel tetrapyridoporphyrin/active carbon Li/SOCl2Battery positive electrode catalytic material, catalytic Li/SOCl2Discharge voltage versus time graph of the battery.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.
Example 1
The invention provides a tetrapyridoporphyrin nickel/active carbon Li/SOCl2The preparation method of the battery carbon anode catalytic material specifically comprises the following steps:
step 1: 1.82g of 2, 3-pyridinedicarboxylic acid, 2.05g of urea, 0.98g of nickel chloride hexahydrate, 0.39g of ammonium molybdate tetrahydrate and 0.23g of a specific surface area of 1400m2The activated carbon is mixed and fully and uniformly ground.
Step 2: and (3) placing the mixture in a crucible, transferring the mixture to a muffle furnace, heating the mixture to 140 ℃ from room temperature at the heating rate of 8 ℃/min in the air atmosphere, then preserving the heat for 1h, then heating the mixture to 240 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling the mixture to room temperature to obtain a crude product.
And step 3: grinding the crude product into fine powder in a mortar, washing the fine powder with deionized water for multiple times until the clear liquid is completely clear, then sequentially performing suction filtration with deionized water and absolute ethyl alcohol, and performing vacuum drying at 70 ℃ for 16h to obtain the nickel tetrapyridoporphyrin/active carbon Li/SOCl2A battery positive electrode catalytic material.
Referring to FIG. 1, it can be seen that the IR spectrum of NiTAP/AC is 904cm-1Shows typical vibration peaks of Ni-N bond in NiTAP at 798 and 744cm-1Two vibrational peaks corresponding to the N-H bonds appear. The IR spectrum of NiTAP/AC also showed a C-H (1094 cm) corresponding to that of NiTAP-1)、C＝C(1528cm-1) And C ═ N (1583 and 1634 cm)-1) And (4) an absorption peak is obtained.
Referring to FIG. 2, it can be seen that NiTAP/AC has a bulk structure with uniformly distributed pores of uniform size. NiTAP grows on the AC surface in situ, so that NiTAP accumulation can be effectively prevented.
Referring to FIG. 3, NiTAP/AC catalyzed Li/SOCl can be seen2The voltage platform of the battery is improved, the discharge time is prolonged by 390s, which shows that the addition of the NiTAP/AC catalytic material is beneficial to improving Li/SOCl2Voltage plateau and extended discharge time of the battery.
Example 2
The invention provides a tetrapyridoporphyrin nickel/active carbon Li/SOCl2The preparation method of the battery carbon anode catalytic material specifically comprises the following steps:
step 1: 0.92g of 2, 3-pyridinedicarboxylic acid, 1.55g of urea, 0.68g of nickel chloride hexahydrate, 0.19g of ammonium molybdate tetrahydrate and 0.10g of a specific surface area of 1400m2The activated carbon is mixed and fully and uniformly ground.
Step 2: and (3) placing the mixture in a crucible, transferring the mixture to a muffle furnace, heating the mixture to 120 ℃ from room temperature at the heating rate of 4 ℃/min in the air atmosphere, then preserving the heat for 0.3h, then heating the mixture to 220 ℃ at the heating rate of 6 ℃/min, preserving the heat for 0.5h, and cooling the mixture to room temperature to obtain a crude product.
And step 3: grinding the crude product into fine powder in a mortar, washing the fine powder with deionized water for multiple times until the supernatant is completely clear, and vacuum drying at 70 ℃ for 10h to obtain the nickel tetrapyridoporphyrin/active carbon Li/SOCl2A battery positive electrode catalytic material.
Example 3
The invention provides a tetrapyridoporphyrin nickel/active carbon Li/SOCl2The preparation method of the battery carbon anode catalytic material specifically comprises the following steps:
step 1: 2.12g of 2, 3-pyridinedicarboxylic acid, 3.15g of urea, 1.48g of nickel chloride hexahydrate, 0.59g of ammonium molybdate tetrahydrate and 0.30g of a specific surface area of 1400m2The activated carbon is mixed and fully and uniformly ground.
Step 2: and (3) placing the mixture in a crucible, transferring the mixture to a muffle furnace, heating the mixture to 160 ℃ from room temperature at a heating rate of 10 ℃/min in an air atmosphere, preserving the heat for 50min, then heating the mixture to 300 ℃ at a heating rate of 8 ℃/min, preserving the heat for 2.5h, and cooling the mixture to room temperature to obtain a crude product.
And step 3: grinding the crude product into fine powder in a mortar, washing the fine powder with deionized water for multiple times until the supernatant is completely clear, and vacuum drying at 70 ℃ for 28h to obtain the nickel tetrapyridoporphyrin/active carbon Li/SOCl2A battery positive electrode catalytic material.
Example 4
The invention provides a tetrapyridoporphyrin nickel/active carbon Li/SOCl2The preparation method of the battery carbon anode catalytic material specifically comprises the following steps:
step 1: 1.22g of 2, 3-pyridinedicarboxylic acid, 1.95g of urea, 0.88g of nickel chloride hexahydrate, 0.29g of ammonium molybdate tetrahydrate and 0.15g of a specific surface area of 1400m2The activated carbon is mixed and fully and uniformly ground.
Step 2: and (3) placing the mixture in a crucible, transferring the mixture to a muffle furnace, heating the mixture to 130 ℃ from room temperature at the heating rate of 6 ℃/min in the air atmosphere, then preserving the heat for 0.5h, then heating the mixture to 260 ℃ at the heating rate of 4 ℃/min, preserving the heat for 1h, and cooling the mixture to room temperature to obtain a crude product.
And step 3: grinding the crude product into fine powder in a mortar, washing the fine powder with deionized water for multiple times until the supernatant is completely clear, and vacuum drying at 70 ℃ for 22h to obtain the nickel tetrapyridoporphyrin/active carbon Li/SOCl2A battery positive electrode catalytic material.
Example 5
The invention provides a tetrapyridoporphyrin nickel/active carbon Li/SOCl2The preparation method of the battery carbon anode catalytic material specifically comprises the following steps:
step 1: 1.82g of 2, 3-pyridinedicarboxylic acid, 2.75g of urea, 1.28g of nickel chloride hexahydrate, 0.49g of ammonium molybdate tetrahydrate and 0.25g of a specific surface area of 1400m2The activated carbon is mixed and fully and uniformly ground.
Step 2: and (3) placing the mixture in a crucible, transferring the mixture to a muffle furnace, heating the mixture to 150 ℃ from room temperature at the heating rate of 9 ℃/min in the air atmosphere, preserving the heat for 40min, then heating the mixture to 280 ℃ at the heating rate of 10 ℃/min, preserving the heat for 3h, and cooling the mixture to room temperature to obtain a crude product.
And step 3: grinding the crude product into fine powder in a mortar, washing the fine powder with deionized water for multiple times until the supernatant is completely clear, and vacuum drying at 70 ℃ for 22h to obtain the nickel tetrapyridoporphyrin/active carbon Li/SOCl2A battery positive electrode catalytic material.
In conclusion, the method has novel design idea, and the NiTAP/AC nano composite material can be prepared by adopting an in-situ solid phase method in an air atmosphere. Asphalt coke activated carbon matched with acetylene black is used as a template to induce and generate a nano-scale catalytic material, so that the conductivity of the catalytic material is improved while active sites are fully exposed, and the SOCl is enhanced2The surface of (2) catalyzes the reduction reaction. The method is simple and easy to control, has low cost and high repeatability, and is favorable for industrial production. After the NiTAP/AC catalytic material prepared by the invention is added into the carbon anode, Li/SOCl2The discharge time of the battery is about 1500s, and the discharge voltage platform of the battery is improved. NiTAP/AC can be used as a Li/SOCl2The positive electrode catalytic material of the battery is good.
Claims (5)
1. Tetrapyridoporphyrin nickel/active carbon Li/SOCl2The preparation method of the battery carbon anode catalytic material is characterized in that; the method specifically comprises the following steps:
step 1: according to the mass ratio (0.92-2.12): (1.55-3.15): (0.68-1.48): (0.19-0.59): (0.10-0.30) weighing 2, 3-pyridinedicarboxylic acid, urea, nickel chloride hexahydrate, ammonium molybdate tetrahydrate and asphalt coke activated carbon, mixing and fully grinding uniformly to obtain a mixture;
step 2: in an air atmosphere, heating the mixture from room temperature to 120-160 ℃ at a heating rate of 4-10 ℃/min, then preserving heat for 0.3-1 h, then heating to 220-300 ℃ at a heating rate of 4-10 ℃/min, preserving heat for 0.5-3 h, and cooling to room temperature to obtain a crude product;
and step 3: grinding the crude product, washing and drying to obtain the nickel tetrapyridoporphyrin/active carbonLi/SOCl2A battery positive electrode catalytic material.
2. The tetrapyridoporphyrin nickel/activated carbon Li/SOCl as claimed in claim 12The preparation method of the battery carbon anode catalytic material is characterized by comprising the following steps: the specific surface area of the asphalt coke activated carbon in the step 1 is 1400m2/g。
3. The tetrapyridoporphyrin nickel/activated carbon Li/SOCl as claimed in claim 12The preparation method of the battery carbon anode catalytic material is characterized by comprising the following steps: the washing process in the step 3 is that the washing is carried out for a plurality of times by using deionized water, and then the filtration is carried out by using the deionized water and absolute ethyl alcohol in sequence.
4. The tetrapyridoporphyrin nickel/activated carbon Li/SOCl as claimed in claim 42The preparation method of the battery carbon anode catalytic material is characterized by comprising the following steps: and the drying in the step 3 is vacuum drying at 70 ℃ for 10-28 h.
5. Nickel tetrapyridoporphyrin/active carbon Li/SOCl prepared by the preparation method according to any one of claims 1 to 42The battery anode catalytic material is characterized in that: the catalytic material is a porous structure formed by NiTAP in-situ growth on an AC surface, and the size of the porous structure is consistent and the porous structure is uniformly distributed.
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Application publication date: 20210615 |