CN115206588B - Conductive agent, preparation method thereof and application thereof in alkaline manganese battery - Google Patents

Conductive agent, preparation method thereof and application thereof in alkaline manganese battery Download PDF

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CN115206588B
CN115206588B CN202210850543.7A CN202210850543A CN115206588B CN 115206588 B CN115206588 B CN 115206588B CN 202210850543 A CN202210850543 A CN 202210850543A CN 115206588 B CN115206588 B CN 115206588B
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carbonate
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resin
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CN115206588A (en
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卢其华
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Nanping Yanping Xindonglai Technology Co ltd
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Nanping Yanping Xindonglai Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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
    • H01M4/06—Electrodes for primary cells
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a conductive agent, a preparation method thereof and application thereof in an alkaline manganese battery, wherein the conductive agent comprises a conductive capsule, thermosetting resin, carbonate and a processing aid; the average grain diameter of the conductive capsule is 10-1000 nm, and the conductive capsule is uniformly dispersed in a resin glue solution formed by mixing the thermosetting resin, the carbonic ester and the processing aid; the electrically conductive capsule comprises a capsule core and a capsule wall; the capsule core is a nano conductive particle, and the capsule wall is a conductive polymer; the mass ratio of the nano conductive particles to the conductive polymer is 60-90: 10 to 40. The invention mainly coats and modifies the main conductive component carbon nano particles of the conductive agent through the polymer, greatly improves the dispersion stability of the conductive agent in use or long-time storage, and has positive significance for the manufacturing and processing process of batteries and long-time transportation and storage.

Description

Conductive agent, preparation method thereof and application thereof in alkaline manganese battery
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of batteries, in particular to a conductive agent, a preparation method thereof and application thereof in an alkaline manganese battery.
[ background of the invention ]
The alkaline manganese battery has the characteristics of large discharge power, long shelf life, convenient and quick use, high cost performance and the like, and is always in the leading position in numerous primary batteries. With the wider application range of alkaline manganese batteries, people put higher and higher requirements on the aspects of the improvement of the discharge capacity, the use in a high-power state, the longer storage life, the safety and the like of the alkaline manganese batteries. Therefore, there is a need to optimize the materials, formulations, and structural components of the alkaline manganese battery in order to make the electrode material exert electrical properties to a greater extent, and in particular, there is a need to reduce the internal resistance of the battery and reduce the electrode passivation behavior of the battery during the discharge process.
For the alkaline manganese battery, a certain amount of conductive agent is added in the electrode manufacturing process and is used for increasing the electronic conductivity between active substances and between the active substances and a current collector, a conductive network is formed on the surface of the active substances to accelerate the electron transmission rate, and meanwhile, electrolyte can be absorbed and maintained, so that the alkaline manganese battery has excellent discharge characteristics and longer storage life.
However, the conductive agents currently used are basically carbon materials (such as conductive carbon black and ultrafine graphite powder) with small particle size and large specific surface area, which are particularly prone to agglomeration and difficult dispersion during use, and in the electrode processing process, due to poor compatibility of the inorganic carbon materials with organic resins and active substances, the inorganic carbon materials are very easy to migrate and precipitate from the electrodes, thereby affecting effective exertion of the electrical properties of the active substances and the storage life of the battery.
[ summary of the invention ]
The invention aims to solve the technical problem of providing a conductive agent, a preparation method thereof and application thereof in an alkaline manganese battery, wherein the conductive agent comprises a conductive capsule, thermosetting resin, carbonic ester and a processing aid, wherein the capsule core of the conductive capsule is nano conductive particles, and the capsule wall is a conductive polymer, namely, carbon nano particles serving as a main conductive component of the conductive agent are coated and modified by the polymer, so that the dispersion stability of the conductive agent in the use process or the long-time storage process is greatly improved, and the conductive agent has positive significance for the manufacturing and processing process of the battery and the long-time transportation and storage process.
In a first aspect, the present invention provides a conductive agent comprising a conductive capsule, a thermosetting resin, a carbonate, and a processing aid;
the average particle size of the conductive capsules is 10-1000 nm, and the conductive capsules are uniformly dispersed in a resin glue solution formed by mixing the thermosetting resin, the carbonic ester and the processing aid;
the electrically conductive capsule comprises a capsule core and a capsule wall;
the capsule core is a nano conductive particle, and the capsule wall is a conductive polymer;
the mass ratio of the nano conductive particles to the conductive polymer is 60-90: 10-40.
In a second aspect, the present invention provides a method for preparing a conductive agent, for preparing the conductive agent of the first aspect, the method comprising the steps of:
s1, placing nano conductive particles and a conductive polymer in an organic solvent for ball milling and dispersing to obtain a mixed solution, wherein the mass ratio of the nano conductive particles to the conductive polymer is 60-90: 10-40; conveying the mixed solution into a spray dryer through a peristaltic pump for spray drying to obtain a conductive capsule with the average particle size of 10-1000 nm; the capsule core of the conductive capsule is nano conductive particles, and the capsule wall is a conductive polymer;
s2, dissolving thermosetting resin and a processing aid in the carbonate by using a high-speed shearing machine to obtain a resin glue solution;
and S3, dispersing the conductive capsules in the resin glue solution under the condition of vacuum stirring to obtain the conductive agent.
In a third aspect, the present invention provides an alkali manganese battery comprising the conductive agent of the first aspect.
The invention has the advantages that:
(1) According to the invention, the carbon nanoparticles serving as the main conductive component of the conductive agent are coated and modified by the polymer, a layer of steric hindrance is formed among the carbon nanoparticles, and the problem that secondary aggregation particles are dispersed and re-agglomerated in the physical dispersion process of the carbon nanoparticles can be relieved, so that the dispersion stability of the conductive agent in the use process or the long-time storage process is improved, and the conductive agent has positive significance in the manufacturing and processing process of batteries and long-time transportation and storage.
(2) The structure of the conductive capsule is selected, the capsule core is carbon nano particles, and the capsule wall is a polymer, so that the compatibility between the inorganic carbon material and active substances and organic resin is effectively improved, the migration and precipitation of the inorganic carbon nano particles from the electrode are reduced, and the stable performance of the electrical property of the battery and the long storage life are ensured.
(3) The polymer selected in the preparation of the conductive capsule is a conductive polymer, the conductive polymer with the electron transmission capability higher than that of an inorganic carbon nano material is selected, so that the electronic conductivity of an electrode is favorably improved, and meanwhile, the carbonate compound solvent selected in the preparation of a conductive agent has better solvating capability on anions and cations of an electrolyte and is favorable for the transmission of ions in the battery, and the measures have positive effects on reducing the internal resistance of the battery.
(4) The conductive agent prepared by the invention is an emulsion conductive agent, and when the conductive agent is used for manufacturing a battery electrode, an active substance can be directly added into the conductive agent, parameters such as solid content, viscosity and the like can be adjusted in a large range according to requirements, so that the conductive agent can adapt to various molding processes of the electrode, and the battery electrode can be more conveniently and efficiently manufactured.
[ description of the drawings ]
The invention will be further described with reference to the following examples with reference to the accompanying drawings.
FIG. 1 is a schematic structural view of a conductive capsule of the present invention;
FIG. 2 is a schematic diagram of the distribution of conductive capsules in a conductive state of the conductive agent of the present invention;
FIG. 3 is a schematic diagram of the distribution of the conductive capsules in the electrodes and the mechanism of the conductive action;
FIG. 4 is an SEM photograph of the emulsion conductive agent prepared in example 1 of the present invention taken after drying;
fig. 5 is an SEM picture taken after drying of the emulsion conductive agent prepared in comparative example 1.
[ detailed description ] embodiments
The embodiment of the invention provides a conductive agent, a preparation method thereof and application thereof in an alkaline manganese battery, wherein the conductive agent comprises a conductive capsule, thermosetting resin, carbonic ester and a processing aid, wherein the capsule core of the conductive capsule is nano conductive particles, and the capsule wall is a conductive polymer, namely, the main conductive component carbon nano particles of the conductive agent are coated and modified by the polymer, so that the dispersion stability of the conductive agent in the use or long-time storage process is greatly improved, and the conductive agent has positive significance for the manufacturing and processing process of the battery and long-time transportation and storage.
In order to solve the above problems, the technical solution in the embodiments of the present invention has the following general idea: the carbon nano particles which are the main conductive component of the conductive agent are coated and modified by the polymer, so that a layer of steric hindrance is formed among the carbon nano particles, the problem that secondary aggregation particles are dispersed and re-aggregated in the physical dispersion process of the carbon nano particles is solved, and the dispersion stability of the conductive agent in use or long-time storage is improved; and the structure of the conductive capsule can effectively improve the compatibility among the inorganic carbon material, the active substance and the organic resin, reduce the migration and precipitation of the inorganic carbon nano particles from the electrode, and ensure the stable performance of the electrical property of the battery and long storage life.
The conductive agent of the embodiment of the invention comprises a conductive capsule, thermosetting resin, carbonate and a processing aid; the conductive agent comprises the following conductive capsules, thermosetting resin, carbonate and a processing aid in a mass ratio: 10-50: 10-40: 40-80: 1-10;
the conductive agent is an emulsion conductive agent.
As shown in fig. 1, the conductive capsule 1 comprises a capsule core 11 and a capsule wall 12; the capsule core 11 is a nano conductive particle, and the capsule wall 12 is a conductive polymer; the mass ratio of the nano conductive particles to the conductive polymer is 60-90: 10-40.
As shown in fig. 2, the conductive capsules 1 have an average particle size of 10 to 1000nm and are uniformly dispersed in a resin glue solution 2 formed by mixing the thermosetting resin, the carbonate and the processing aid.
As shown in fig. 3, the conductive capsule 1 conducts electrons between active material particles 3, and the resin glue solution 2 adheres the nano conductive particles in the capsule core 11 and the active material outside the conductive capsule 1 together to form an electrode.
The nano conductive particles are selected from one or more of conductive carbon black, conductive graphite, carbon nanotubes, graphene and carbon fibers; the conductive polymer is selected from one or more of polyacetylene, polypyrrole, polythiophene, polyphenylene, polyphenylacetylene and polyaniline. The conductive capsule is prepared by performing ball milling dispersion on nano conductive particles and a conductive polymer in an organic solvent to obtain a mixed solution, and feeding the mixed solution into a spray dryer through a peristaltic pump for spray drying.
The thermosetting resin is selected from one or more of phenolic resin, urea resin, melamine-formaldehyde resin, epoxy resin, unsaturated polyester resin, polyurethane and polyimide resin.
The carbonate ester comprises cyclic carbonate ester and chain carbonate ester; the mass ratio of the cyclic carbonate to the chain carbonate is 20-40: 60-80; the cyclic carbonate is selected from one or more of ethylene carbonate and propylene carbonate; the chain carbonate is selected from one or a combination of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
The processing aid is selected from one or more of acetone, butanone, methyl formate, ethyl acetate and methyl acetate.
The preparation method of the conductive agent in the embodiment of the invention comprises the following steps:
a preparation method of a conductive agent comprises the following steps:
s1, placing nano conductive particles and a conductive polymer in an organic solvent for ball milling and dispersing to obtain a mixed solution, wherein the mass ratio of the nano conductive particles to the conductive polymer is as follows: 60-90: 10-40; feeding the mixed solution into a spray dryer through a peristaltic pump for spray drying to obtain conductive capsules with the average particle size of 10-1000 nm; the capsule core of the conductive capsule is nano conductive particles, and the capsule wall is a conductive polymer.
Wherein, the average grain diameter of the conductive capsule can be controlled by controlling the material concentration, the feeding speed, the drying temperature, the airflow pressure and the caliber of the nozzle; when the organic solvent is acetone, the inlet temperature and the outlet temperature of the spray dryer are preferably set to 120 ℃ and 80 ℃ respectively;
s2, dissolving thermosetting resin and a processing aid in the carbonic ester by using a high-speed shearing machine to obtain a resin glue solution; the rotating speed of the high-speed shearing machine is 2000-4000 rpm.
And S3, dispersing the conductive capsules in the resin glue solution under the vacuum stirring condition to obtain the emulsion conductive agent.
The main applications of the conductive agent in the embodiment of the invention are as follows:
the conductive agent is applied to the production and the manufacture of alkaline manganese batteries, such as the manufacture of positive electrodes and negative electrodes of LR6 alkaline zinc-manganese batteries.
For better understanding of the above technical solutions, the following detailed descriptions will be provided in conjunction with the drawings and the detailed description of the embodiments.
Example 1
The conductive agent of the present embodiment includes 30 parts by mass of a conductive capsule, 20 parts by mass of an epoxy resin, 50 parts by mass of a carbonate, and 5 parts by mass of ethyl acetate; the capsule core of the conductive capsule is conductive carbon black, the capsule wall is polyaniline, and the carbonate is prepared by compounding ethylene carbonate and dimethyl carbonate according to a mass ratio of 30.
The preparation method of the conductive agent of the embodiment is as follows:
(1) Adding conductive carbon black and polyaniline into an acetone solvent according to the mass ratio of 70: 30, performing ball milling dispersion for 2 hours to obtain a mixed solution, conveying the mixed solution into a spray dryer through a peristaltic pump for spray drying, setting the inlet temperature and the outlet temperature of the spray dryer to be 120 ℃ and 80 ℃ respectively, and quickly evaporating acetone to dryness to obtain a conductive capsule with the average particle size of 150 nm;
(2) Dissolving epoxy resin and ethyl acetate in the carbonic ester by using a high-speed shearing machine with the rotating speed of 3000rpm to obtain epoxy resin glue solution;
(3) And (3) dispersing the conductive capsules obtained in the step (1) into the epoxy resin glue solution obtained in the step (2) in proportion under the vacuum stirring condition to obtain the conductive agent.
Further, the conductive agent is applied to the manufacture of the positive electrode of an LR6 alkaline zinc-manganese battery.
Example 2
The conductive agent of the present embodiment includes 25 parts by mass of a conductive capsule, 25 parts by mass of a phenol resin, 60 parts by mass of a carbonate, and 2 parts by mass of acetone; wherein the capsule core of the conductive capsule is conductive graphite, and the capsule wall is polythiophene; the carbonate is compounded by ethylene carbonate and dimethyl carbonate with the mass ratio of 30.
The preparation method of the conductive agent of the embodiment is as follows:
(1) Adding conductive graphite and polythiophene into an acetone solvent according to the mass ratio of 65: 35, performing ball milling dispersion for 2 hours to obtain a mixed solution, conveying the mixed solution into a spray dryer through a peristaltic pump for spray drying, setting the inlet temperature and the outlet temperature of the spray dryer to be 120 ℃ and 80 ℃ respectively, and quickly evaporating the acetone to dryness to obtain a conductive capsule with the average particle size of 300 nm;
(2) Dissolving phenolic resin and acetone in the carbonate by using a high-speed shearing machine with the rotating speed of 2000rpm to obtain phenolic resin glue solution;
(3) And (3) dispersing the conductive capsules in the step (1) into the phenolic resin glue solution in the step (2) in proportion under the condition of vacuum stirring to obtain the conductive agent.
Further, the conductive agent is applied to the manufacture of the negative electrode of an LR6 alkaline zinc-manganese battery.
Example 3
The conductive agent of the present example includes 25 parts by mass of a conductive capsule, 20 parts by mass of an unsaturated polyester resin, 45 parts by mass of a carbonate ester and 10 parts by mass of methyl formate, 5 parts by mass of acetone; wherein the capsule core of the conductive capsule is a carbon nano tube, and the capsule wall is polyphenylene; the carbonate is prepared by compounding ethylene carbonate and methyl ethyl carbonate with the mass ratio of 30.
The preparation method of the conductive agent of the embodiment is as follows:
(1) Adding carbon nano tubes and polyphenylene into an acetone solvent according to the mass ratio of 60: 40, carrying out ball milling and dispersing for 2 hours to obtain a mixed solution, conveying the mixed solution into a spray dryer through a peristaltic pump for spray drying, setting the inlet temperature and the outlet temperature of the spray dryer to be 120 ℃ and 80 ℃ respectively, and quickly evaporating acetone to dryness to obtain a conductive capsule with the average particle size of 500 nm;
(2) Dissolving unsaturated polyester resin, methyl formate and acetone in the carbonic ester by using a high-speed shearing machine with the rotating speed of 3000rpm to obtain unsaturated polyester resin glue solution;
(3) And (3) dispersing the conductive capsules obtained in the step (1) into the unsaturated polyester resin glue solution obtained in the step (2) in proportion under the condition of vacuum stirring to obtain the conductive agent.
Further, the conductive agent is applied to the manufacture of the positive electrode of an LR6 alkaline zinc-manganese battery.
Example 4
The conductive agent of the embodiment comprises 10 parts by mass of a conductive capsule, 40 parts by mass of epoxy resin, 40 parts by mass of carbonate and 10 parts by mass of ethyl acetate, wherein the capsule core of the conductive capsule is graphene, and the capsule wall is polyphenylacetylene; the carbonate is prepared by compounding ethylene carbonate and diethyl carbonate with the mass ratio of 40.
The preparation method of the conductive agent of the embodiment is as follows:
(1) Adding graphene and polyphenylacetylene into an acetone solvent according to a mass ratio of 90:10, performing ball milling dispersion for 2 hours to obtain a mixed solution, conveying the mixed solution into a spray dryer through a peristaltic pump for spray drying, setting the inlet temperature and the outlet temperature of the spray dryer to be 120 ℃ and 80 ℃ respectively, and quickly evaporating acetone to dryness to obtain a conductive capsule with the average particle size of 700 nm;
(2) Dissolving unsaturated polyester resin, methyl formate and acetone in the carbonic ester by using a high-speed shearing machine with the rotating speed of 4000rpm to obtain unsaturated polyester resin glue solution;
(3) And (3) dispersing the conductive capsules obtained in the step (1) into the unsaturated polyester resin glue solution obtained in the step (2) in proportion under the condition of vacuum stirring to obtain the conductive agent.
Further, the conductive agent is applied to the manufacture of the positive electrode of an LR6 alkaline zinc-manganese battery.
Example 5
The conductive agent of the embodiment comprises 50 parts by mass of a conductive capsule, 10 parts by mass of epoxy resin, 80 parts by mass of carbonate and 1 part by mass of ethyl acetate, wherein the capsule core of the conductive capsule is carbon fiber, and the capsule wall is polypyrrole; the carbonate is prepared by compounding 20 mass percent of propylene carbonate and 80 mass percent of ethyl methyl carbonate.
The preparation method of the conductive agent of the embodiment is as follows:
(1) Adding carbon fiber and polypyrrole into an acetone solvent according to a mass ratio of 80: 20, performing ball milling and dispersing for 2 hours to obtain a mixed solution, conveying the mixed solution into a spray dryer through a peristaltic pump for spray drying, setting the inlet temperature and the outlet temperature of the spray dryer to be 120 ℃ and 80 ℃ respectively, and quickly evaporating acetone to dryness to obtain a conductive capsule with the average particle size of 1000 nm;
(2) Dissolving unsaturated polyester resin, methyl formate and acetone in the carbonic ester by using a high-speed shearing machine with the rotating speed of 2500rpm to obtain unsaturated polyester resin glue solution;
(3) And (3) dispersing the conductive capsules obtained in the step (1) into the unsaturated polyester resin glue solution obtained in the step (2) in proportion under the condition of vacuum stirring to obtain the conductive agent.
Further, the conductive agent is applied to the manufacture of the positive electrode of an LR6 alkaline zinc-manganese battery.
Comparative example 1
This comparative example is different from example 1 in that a conductive agent was directly prepared using conductive carbon black instead of the conductive capsule, and the rest was the same. Namely, the conductive agent of the present comparative example includes 30 parts by mass of conductive carbon black, 20 parts by mass of epoxy resin, 50 parts by mass of carbonate, and 5 parts by mass of ethyl acetate; wherein the carbonate is prepared by compounding ethylene carbonate and dimethyl carbonate with the mass ratio of 30.
The preparation method of the conductive agent of this comparative example was as follows:
(1) Dissolving phenolic resin and acetone in carbonic ester by using a high-speed shearing machine with the rotating speed of 2000rpm to obtain phenolic resin glue solution;
(2) And (2) dispersing conductive carbon black in the phenolic resin glue solution obtained in the step (1) in proportion under the vacuum stirring condition to obtain the conductive agent.
Further, the conductive agent is applied to the manufacture of the positive electrode of an LR6 alkaline zinc-manganese battery.
Comparative example 2
The comparative example is different from comparative example 1 in that the comparative example uses ultrafine graphite powder instead of conductive carbon black to prepare a conductive agent; the rest is the same.
Comparative example 3
This comparative example is different from example 1 in that polyvinylpyrrolidone was used as the capsule wall instead of polyaniline, and the rest was the same.
Comparative example 4
The comparative example is different from example 1 in that diethyl carbonate is used instead of the compound carbonate of ethylene carbonate and dimethyl carbonate in the mass ratio of 30.
Comparative example 5
The comparative example differs from example 1 in that ethylene carbonate is used instead of a compound carbonate of ethylene carbonate and dimethyl carbonate in a mass ratio of 30.
Comparative example 6
The difference between the comparative example and the example 1 is that propylene carbonate is used to replace the compound carbonic ester of ethylene carbonate and dimethyl carbonate with the mass ratio of 30.
Comparative example 7
The present comparative example is different from example 1 in that it uses ultrafine graphite powder instead of conductive carbon black to prepare a conductive agent; and propylene carbonate is used for replacing ethylene carbonate and dimethyl carbonate compound carbonate with the mass ratio of 30.
The conductive agents prepared in example 1 and comparative example 1 were observed for dispersion, and their scanning electron microscope images were respectively shown in fig. 4 and 5.
The alkaline zinc-manganese batteries manufactured in examples 1 to 5 and comparative examples 1 to 6 were tested for electrical properties, 9 batteries were taken in each test group, and the average value was taken as the test result, and the results are shown in table 1, and the specific tests are as follows:
the AC impedance value: discharging the cell at 20 deg.C at a current of 250mA to 50% SOC, applying a voltage of 10mV to the cell, sweeping at a frequency in the range of 0.1Hz-100KHz, and recording the impedance value;
initial-stage battery discharge time: the test temperature is 20 ℃, and discharge is carried out under the conditions that the discharge current and the cut-off voltage are respectively 250mA and 0.8V;
battery discharge time after storage: storing the battery in an environment with the relative humidity of less than 75% at the temperature of below 35 ℃ for 3 months, and then discharging under the conditions that the test temperature is 20 ℃ and the discharge current and the cut-off voltage are respectively 250mA and 0.8V;
capacity retention ratio of storage battery: the percentage of the discharge time of the storage battery to the discharge time of the initial battery is taken as the capacity retention rate of the storage battery.
TABLE 1 alkaline Zinc-manganese cell Performance test results
Figure BDA0003754450150000101
Figure BDA0003754450150000111
As can be seen from the SEM images of fig. 4 and 5, the dispersing effect of the conductive agent prepared in example 1 is significantly better than that of comparative example 1, which indicates that preparing the conductive carbon material into the conductive capsule is beneficial to improving the interface effect and improving the dispersion stability of the conductive capsule in the electrode.
From the results of table 1, it can be seen that:
compared with comparative examples 1 to 7, the impedance values of examples 1 to 5 are relatively small, and the initial-period battery discharge time, the post-storage battery discharge time and the storage battery capacity retention rate are high;
the impedance values of examples 1 to 5 are relatively small compared to those of comparative examples 1 to 7, indicating that the conductive capsules made of the conductive polymer are advantageous in reducing the internal resistance of the battery;
compared with the comparative example 3, if the non-conductive polymer polyvinylpyrrolidone is changed to be used as the capsule wall in the example 1, the electron transmission of the conductive particles among active substances is hindered, the internal resistance of the battery is increased, and the discharge performance of the battery is influenced;
compared with comparative examples 4-6, in examples 1-5, the compound of the cyclic carbonate and the chain carbonate is used as a solvent, so that the synergistic effect of the cyclic carbonate and the chain carbonate on ion solvation is effectively exerted, the resistance of anion and cation transmission in the battery is reduced, and the discharge service time of the battery is prolonged; according to the comparison of the discharge time of the battery in the initial period of the battery test, the conductive agent disclosed by the invention is beneficial to exerting the performance of the active material of the battery to a greater extent, so that the alkaline zinc-manganese battery shows a greater discharge capacity, and meanwhile, because the prepared electrode has good stability, the storage capacity retention rate of the battery is also improved, and the storage life of the battery is improved.
Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.

Claims (9)

1. An electroconductive agent characterized by: comprises conductive capsules, thermosetting resin, carbonate and processing aid;
the average grain diameter of the conductive capsule is 10-1000nm, and the conductive capsule is uniformly dispersed in a resin glue solution formed by mixing the thermosetting resin, the carbonate and the processing aid;
the conductive capsule comprises a capsule core and a capsule wall;
the capsule core is a nano conductive particle, and the capsule wall is a conductive polymer;
the mass ratio of the nano conductive particles to the conductive polymer is 60-90: 10-40;
the nano conductive particles are selected from one or more of conductive carbon black, conductive graphite, carbon nanotubes, graphene and carbon fibers;
the conductive polymer is selected from one or more of polyacetylene, polypyrrole, polythiophene, polyphenylene, polyphenylacetylene and polyaniline.
2. A conductive agent as defined in claim 1, wherein:
the conductive agent comprises the following conductive capsules, thermosetting resin, carbonate and a processing aid in a mass ratio: 10-50: 10-40: 40-80: 1-10;
the thermosetting resin is selected from one or more of phenolic resin, urea resin, melamine-formaldehyde resin, epoxy resin, unsaturated polyester resin, polyurethane and polyimide resin;
the carbonate ester comprises cyclic carbonate ester and chain carbonate ester; the mass ratio of the cyclic carbonate to the chain carbonate is 20-40: 60-80; the cyclic carbonate is selected from one or more of ethylene carbonate and propylene carbonate; the chain carbonate is selected from one or a combination of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate;
the processing aid is selected from one or more of acetone, butanone, methyl formate, ethyl acetate and methyl acetate.
3. A conductive agent as defined in claim 1, wherein: the conductive capsule is prepared by the following method: and carrying out ball milling dispersion on the nano conductive particles and the conductive polymer in an organic solvent to obtain a mixed solution, and conveying the mixed solution into a spray dryer through a peristaltic pump for spray drying to obtain the conductive capsule.
4. A conductive agent as defined in claim 1, wherein: the conductive agent is an emulsion conductive agent.
5. A preparation method of a conductive agent is characterized by comprising the following steps: for the preparation of the conductive agent as claimed in any one of claims 1 to 4, the preparation method comprising the steps of:
s1, placing nano conductive particles and a conductive polymer in an organic solvent for ball milling and dispersing to obtain a mixed solution, wherein the mass ratio of the nano conductive particles to the conductive polymer is as follows: 60 to 90:10 to 40; sending the mixed solution into a spray dryer through a peristaltic pump for spray drying to obtain a conductive capsule with the average particle size of 10-1000nm; the capsule core of the conductive capsule is nano conductive particles, and the capsule wall is a conductive polymer; the nano conductive particles are selected from one or more of conductive carbon black, conductive graphite, carbon nanotubes, graphene and carbon fibers; the conductive polymer is selected from one or more of polyacetylene, polypyrrole, polythiophene, polyphenylene, polyphenylacetylene and polyaniline;
s2, dissolving thermosetting resin and a processing aid in the carbonate by using a high-speed shearing machine to obtain a resin glue solution;
and S3, dispersing the conductive capsules in the resin glue solution under the condition of vacuum stirring to obtain the conductive agent.
6. The method for producing a conductive agent according to claim 5, wherein:
the conductive agent comprises the following conductive capsules, thermosetting resin, carbonate and a processing aid in a mass ratio: 10-50: 10-40: 40-80: 1-10;
the thermosetting resin is selected from one or more of phenolic resin, urea resin, melamine-formaldehyde resin, epoxy resin, unsaturated polyester resin, polyurethane and polyimide resin;
the carbonate ester comprises cyclic carbonate ester and chain carbonate ester; the mass ratio of the cyclic carbonate to the chain carbonate is 20 to 40: 60 to 80; the cyclic carbonate is selected from one or more of ethylene carbonate and propylene carbonate; the chain carbonate is selected from one or a combination of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate;
the processing aid is selected from one or more of acetone, butanone, methyl formate, ethyl acetate and methyl acetate.
7. The method for producing a conductive agent according to claim 5, wherein:
when the organic solvent is acetone, the inlet temperature and the outlet temperature of the spray dryer are respectively set to be 120 ℃ and 80 ℃;
the rotating speed of the high-speed shearing machine is 2000-4000 rpm.
8. The method for producing a conductive agent according to claim 5, wherein: the method is characterized in that: the conductive agent is an emulsion conductive agent.
9. An alkaline manganese cell, characterized by: the alkaline manganese cell comprising the conductive agent of any one of claims 1-4.
CN202210850543.7A 2022-07-20 2022-07-20 Conductive agent, preparation method thereof and application thereof in alkaline manganese battery Active CN115206588B (en)

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