CN114989642B - Conductive carbon black modification method, modified conductive carbon black, positive plate and battery - Google Patents

Conductive carbon black modification method, modified conductive carbon black, positive plate and battery Download PDF

Info

Publication number
CN114989642B
CN114989642B CN202210681592.2A CN202210681592A CN114989642B CN 114989642 B CN114989642 B CN 114989642B CN 202210681592 A CN202210681592 A CN 202210681592A CN 114989642 B CN114989642 B CN 114989642B
Authority
CN
China
Prior art keywords
carbon black
conductive carbon
water bath
modified
dispersing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210681592.2A
Other languages
Chinese (zh)
Other versions
CN114989642A (en
Inventor
晁广召
黄圣华
刘娇
郝鑫
胡大林
廖兴群
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huizhou Highpower Technology Co Ltd
Original Assignee
Huizhou Highpower Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huizhou Highpower Technology Co Ltd filed Critical Huizhou Highpower Technology Co Ltd
Priority to CN202210681592.2A priority Critical patent/CN114989642B/en
Publication of CN114989642A publication Critical patent/CN114989642A/en
Application granted granted Critical
Publication of CN114989642B publication Critical patent/CN114989642B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention discloses a conductive carbon black modification method, modified conductive carbon black, a positive plate and a battery, which comprises the following steps: dispersing conductive carbon black in an alcoholizing agent, stirring and dispersing the conductive carbon black, and then carrying out water bath to alcoholize the conductive carbon black; separating out the conductive carbon black in the alcoholizing agent to obtain the conductive carbon black with hydroxyl groups on the surface after alcoholizing; dispersing alcoholized conductive carbon black in ethanol solution, adding a surface modifier, and carrying out water bath to enable the surface modifier to be hydrolyzed and then coated and grafted on the surface of the conductive carbon black; and separating out the conductive carbon black in the ethanol solution to obtain the modified conductive carbon black with the surface modified. The dispersion uniformity of the conductive carbon black in the positive plate is improved, the aggregation of the conductive carbon black is effectively reduced, the situation that the conductive carbon black is separated from a bonding agent in the aging process of the battery is effectively relieved, the continuity of an electronic path is ensured, the internal resistance growth rate of the positive plate is effectively reduced, and the overall performance of the battery is further improved.

Description

Conductive carbon black modification method, modified conductive carbon black, positive plate and battery
Technical Field
The invention relates to the technical field of preparation of battery conductive materials, in particular to a conductive carbon black modification method, modified conductive carbon black, a positive plate and a battery.
Background
The conductive carbon black (Super P, SP for short) has excellent optical, chemical and thermodynamic properties, has wide application in various fields such as batteries, electrocatalysis and the like due to high specific surface and excellent conductive performance, and particularly in recent years, the demand for the conductive carbon black is increased day by day along with the explosive growth of new energy batteries.
However, the surface of the current nanoscale conductive carbon black has extremely high specific surface energy, as shown in fig. 2, the conductive carbon black is easily agglomerated into large particles due to larger van der Waals attraction, the conductive carbon black is more difficult to disperse in a glue solution, the wettability and compatibility of the conductive carbon black and a matrix are poor, and a good interface is difficult to establish with the matrix. In addition, as shown in fig. 1, as the temperature changes and the battery ages, the binder is "fatigued" and physically cohesiveness is reduced, conductive particles are gradually separated from the binder, the conductive agent is gradually deactivated, the internal resistance of the battery increases, polarization increases, and the battery performance is significantly attenuated.
Disclosure of Invention
The invention aims to provide a conductive carbon black modification method, modified conductive carbon black, a positive plate and a battery, which are used for improving the dispersion uniformity of the conductive carbon black in the positive plate, relieving the separation phenomenon of a conductive agent and polyvinylidene fluoride caused by fatigue of a binder, ensuring the continuity of an electronic path, reducing the impedance growth rate of the positive plate and further improving the performance of the battery.
The invention discloses a conductive carbon black modification method, which comprises the following steps:
dispersing conductive carbon black in an alcoholizing agent, stirring and dispersing the conductive carbon black, and then carrying out water bath to alcoholize the conductive carbon black;
separating out the conductive carbon black in the alcoholizing agent to obtain the conductive carbon black with hydroxyl groups on the surface after alcoholizing;
Dispersing alcoholized conductive carbon black in ethanol solution, adding a surface modifier, and carrying out water bath to enable the surface modifier to be hydrolyzed and then coated and grafted on the surface of the conductive carbon black;
and separating out the conductive carbon black in the ethanol solution to obtain the modified conductive carbon black with the surface modified.
Optionally, the surface modifier is an oxy-based, epoxy-based coupling agent.
Alternatively, the surface modifier is gamma-aminopropyl triethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane or gamma-methacryloxypropyl trimethoxysilane.
Optionally, the alcoholizing agent is hydrogen peroxide, concentrated sulfuric acid, concentrated nitric acid, alcohols or weak acid.
Optionally, the alcoholizing agent has a water bath temperature of 35-50deg.C and a water bath time of 1-10 min.
Optionally, the water bath temperature of the ethanol solution is 70-85 ℃ and the water bath time is 8-13 min.
Optionally, dispersing the alcoholized conductive carbon black in ethanol solution, adding a surface modifier, and performing water bath to make the surface modifier hydrolyzed and coated and grafted on the surface of the conductive carbon black, and the method further comprises the steps of: water is added to the ethanol solution to promote sufficient hydrolysis of the surface modifying agent.
The invention also discloses modified conductive carbon black, which is prepared by the conductive carbon black modification method.
The invention also discloses a positive plate which comprises the modified conductive carbon black and polyvinylidene fluoride.
The invention also discloses a battery, which comprises the positive plate.
According to the conductive carbon black modification method, after the conductive carbon black is alcoholized, a surface modifier is added for water bath, so that the surface modifier is hydrolyzed and then coated and grafted on the surface of the conductive carbon black, and the conductive carbon black is subjected to chemical coating modification. As shown in fig. 2, the modified conductive carbon black subjected to surface modification can generate a chemical bonding effect with polyvinylidene fluoride (PVDF), the surface modifier acts as a bridge effect between the conductive carbon black and the PVDF glue, so that the dispersion uniformity of the conductive carbon black in a positive plate is effectively improved, the aggregation of the conductive carbon black is effectively reduced, H atoms of-NH 2 on the surface of the surface modifier can be attracted by F atoms with negative electricity of the PVDF, and the H atoms and the F atoms can form an acting force similar to hydrogen bonds, so that the dispersion uniformity of the conductive carbon black in the preparation process of the positive plate can be improved, the effects of the conductive carbon black and the PVDF can be enhanced, the separation condition of the conductive carbon black from the adhesive fatigue in the aging process of a battery can be effectively relieved, the continuity of an electronic path can be ensured, the internal resistance growth rate of the positive plate can be effectively reduced, and the overall performance of the battery can be further improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention. It is evident that the figures in the following description are only some embodiments of the invention, from which other figures can be obtained without inventive effort for a person skilled in the art. In the drawings:
FIG. 1 is a schematic illustration of the process of bonding and releasing PVDF to conductive carbon black without surface modification;
FIG. 2 is a schematic illustration of conductive carbon black agglomeration without surface modification;
FIG. 3 is a schematic illustration of the surface-modified conductive carbon black bonded to PVDF and not easily detached;
FIG. 4 is a schematic illustration of the uniform dispersion of the surface-modified conductive carbon black according to the embodiment of the present invention;
FIG. 5 is a graph showing energy retention before and after modification of conductive carbon black in accordance with an embodiment of the present invention;
FIG. 6 is a graph showing ACR growth rates before and after modification of conductive carbon black in accordance with an embodiment of the present invention.
Detailed Description
It is to be understood that the terminology used herein, the specific structural and functional details disclosed are merely representative for the purpose of describing particular embodiments, but that the invention may be embodied in many alternate forms and should not be construed as limited to only the embodiments set forth herein.
The invention is described in detail below with reference to the attached drawings and alternative embodiments.
As an embodiment of the present invention, a conductive carbon black modification method is disclosed, comprising the steps of:
s100: dispersing conductive carbon black in an alcoholizing agent, stirring and dispersing the conductive carbon black, and then carrying out water bath to alcoholize the conductive carbon black;
S200: separating out the conductive carbon black in the alcoholizing agent to obtain the conductive carbon black with hydroxyl groups on the surface after alcoholizing;
s300: dispersing alcoholized conductive carbon black in ethanol solution, adding a surface modifier, and carrying out water bath to enable the surface modifier to be hydrolyzed and then coated and grafted on the surface of the conductive carbon black;
S400: and separating out the conductive carbon black in the ethanol solution to obtain the modified conductive carbon black with the surface modified.
According to the conductive carbon black modification method, after the conductive carbon black is alcoholized, a surface modifier is added for water bath, so that the surface modifier is hydrolyzed and then coated and grafted on the surface of the conductive carbon black, and the conductive carbon black is subjected to chemical coating modification. As shown in fig. 3, the modified conductive carbon black subjected to surface modification can generate a chemical bonding effect with polyvinylidene fluoride (PVDF), the surface modifier acts as a bridge effect between the conductive carbon black and the PVDF glue, so that the dispersion uniformity of the conductive carbon black in a positive plate is effectively improved, the aggregation of the conductive carbon black is effectively reduced, the H atoms of-NH 2 on the surface of the surface modifier can be attracted by F atoms with negative electricity of the PVDF, and the H atoms and the F atoms can form an acting force similar to hydrogen bonds, so that the dispersion uniformity of the conductive carbon black in the preparation process of the positive plate can be improved, the effect of the conductive carbon black and the PVDF can be enhanced, the separation condition of the conductive carbon black from the adhesive in the aging process of the battery can be effectively relieved, the continuity of an electronic path is ensured, the internal resistance growth rate of the positive plate is effectively reduced, and the overall performance of the battery is further improved.
Specifically, the surface modifier is an oxy group and an epoxy group coupling agent. More specifically, the surface modifier is gamma-aminopropyl triethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane or gamma-methacryloxypropyl trimethoxysilane. The hydroxyl group of the conductive carbon black reacts with the hydroxyl group of the hydrolyzed gamma-aminopropyl triethoxy silane to form an ether bond, so that the hydrolyzed gamma-aminopropyl triethoxy silane is coated and grafted on the surface of the conductive carbon black.
Specifically, the alcoholizing agent is hydrogen peroxide, concentrated sulfuric acid, concentrated nitric acid, alcohols or weak acid.
Specifically, in step S100, the water bath temperature of the alcoholizing agent is 35 ℃ to 50 ℃, preferably 40 ℃; the water bath time is 1min-10min, preferably 3min. Specifically, the alcoholizing agent is hydrogen peroxide, and the mass fraction of the hydrogen peroxide is 5-15 wt%, preferably 5-8 wt%. The mass ratio of the conductive carbon black to the hydrogen peroxide is (1:10) - (1:5), and is preferably 1:7.
Specifically, in step S200, the alcoholizing agent and the conductive carbon black are filtered with filter paper, washed 2 times with clean water, and dried for 10 hours at 50 ℃ to obtain the conductive carbon black with hydroxyl groups after surface alcoholization.
Specifically, in step S300, the alcoholized conductive carbon black is dispersed in an ethanol solution, and ultrasonic dispersion is performed for 5min, wherein the mass ratio of ethanol to alcoholized carbon black is (1:10) - (1:5); adding gamma-aminopropyl triethoxysilane into the solution after ultrasonic treatment, wherein the mass ratio of the gamma-aminopropyl triethoxysilane to the carbon black is 1:100-1:50. the water bath temperature of the ethanol solution is 70-85 ℃, preferably 80 ℃; the water bath time is 8min-13min, preferably 10min.
More specifically, in step S300, the steps further include: water is added to the ethanol solution to promote sufficient hydrolysis of the surface modifying agent. The addition of water ensures that the surface modifying agent, such as gamma-aminopropyl triethoxysilane, is sufficiently hydrolysed. The added water may be distilled water.
Specifically, in step S400, after the ethanol solution is cooled to room temperature, suction filtration is performed, cleaning is performed with clean water, and drying is performed for 10 hours at 50 ℃ to obtain the modified conductive carbon black with modified surface.
The invention also discloses modified conductive carbon black, which is prepared by the conductive carbon black modification method.
The invention also discloses a positive plate which comprises the modified conductive carbon black and polyvinylidene fluoride. Specifically, the positive plate further comprises a positive electrode material, a positive electrode current collector and a nanotube.
More specifically, the positive electrode material includes one or more of lithium cobaltate, lithium iron phosphate, lithium manganate, lithium titanate, and mixed ternary materials; the thickness of the positive plate is 10 μm-1000 μm.
When the positive plate is prepared, polyvinylidene fluoride is placed in N-methyl pyrrolidone (NMP) to be stirred at a proper rotating speed, so that the polyvinylidene fluoride is ensured to be uniformly dispersed in the N-methyl pyrrolidone. And adding the anode active material, the modified conductive carbon black and the carbon nano tube into the polyvinylidene fluoride glue solution according to proper sequence, stirring at proper rotating speed for proper time, coating by a coating machine, baking at proper temperature, rolling and cutting.
As shown in fig. 3, the modified conductive carbon black subjected to surface modification can have a chemical bonding effect with polyvinylidene fluoride (PVDF), the surface modifier acts as a bridge effect between the conductive carbon black and the PVDF, so that the dispersion uniformity of the conductive carbon black in the positive plate is effectively improved, the aggregation of the conductive carbon black is effectively reduced, H atoms of-NH 2 on the surface of the surface modifier can be attracted by F atoms with negative electricity of the PVDF, and the F atoms with negative electricity form an acting force similar to a hydrogen bond, so that on one hand, the dispersion uniformity of the conductive carbon black in the preparation process of the positive plate can be improved, on the other hand, the effect of the conductive carbon black and the PVDF can be enhanced, the separation condition of the conductive carbon black from an adhesive in the aging process of a battery can be effectively relieved, the continuity of an electronic path can be ensured, the internal resistance growth rate of the positive plate can be effectively reduced, and the overall performance of the battery can be further improved.
The invention also discloses a battery, which comprises the positive plate.
The following is a description of specific examples.
Example 1
Dispersing conductive carbon black in 8wt% hydrogen peroxide, wherein the mass ratio of the conductive carbon black to the hydrogen peroxide is 1:7, stirring in a water bath at the stirring speed of 10r/s after stirring and dispersing the suspension, and the water bath temperature is 40 ℃ and the water bath time is 3min;
Filtering the solid-liquid mixture with proper filter paper, washing with clean water for 2 times, and drying at 50 ℃ for 10 hours to obtain conductive carbon black with alcoholized surface;
Dispersing the alcoholized carbon black in an ethanol solution, and placing the ethanol solution in an ultrasonic water tank for ultrasonic dispersion for 5min, wherein the mass ratio of ethanol to alcoholized carbon black is 1:5, a step of; adding gamma-aminopropyl triethoxysilane into the ultrasonic solution, wherein the mass ratio of the gamma-aminopropyl triethoxysilane to the carbon black is 1:50, adding a proper amount of distilled water at the same time, stirring slowly for 1min, and standing for 30min to ensure that the gamma-aminopropyl triethoxysilane is fully hydrolyzed;
Carrying out water bath on the mixed solution, wherein the water bath temperature is 80 ℃, the water bath is carried out for 10min, cooling to room temperature, carrying out suction filtration, cleaning with clean water, and drying for 10h in a 50 ℃ environment to obtain the surface modified conductive carbon black;
Placing PVDF in NMP for stirring at a proper rotating speed, and ensuring that PVDF is uniformly dispersed in NMP;
And adding the anode active material, the modified conductive carbon black and the carbon nano tube into the PVDF glue solution in proper sequence, stirring at proper rotation speed for proper time, coating by a coating machine, baking at proper temperature, rolling, cutting and preparing the anode plate.
Example 2
Dispersing conductive carbon black in 8wt% hydrogen peroxide, wherein the mass ratio of the conductive carbon black to the hydrogen peroxide is 1:7, stirring in a water bath at the stirring speed of 10r/s after stirring and dispersing the suspension, and the water bath temperature is 40 ℃ and the water bath time is 3min;
Filtering the solid-liquid mixture with proper filter paper, washing with clean water for 2 times, and drying at 50 ℃ for 10 hours to obtain conductive carbon black with alcoholized surface;
Dispersing the alcoholized carbon black in an ethanol solution, and placing the ethanol solution in an ultrasonic water tank for ultrasonic dispersion for 5min, wherein the mass ratio of ethanol to alcoholized carbon black is 1:5, a step of; adding gamma- (2, 3-glycidoxy) propyl trimethoxy silane into the ultrasonic solution, wherein the mass ratio of the gamma- (2, 3-glycidoxy) propyl trimethoxy silane to the carbon black is 1:50, adding a proper amount of distilled water at the same time, stirring for 1min at a slow speed, and standing for 30min to ensure that the gamma-aminopropyl triethoxysilane is fully hydrolyzed;
Carrying out water bath on the mixed solution, wherein the water bath temperature is 80 ℃, the water bath is carried out for 10min, cooling to room temperature, carrying out suction filtration, cleaning with clean water, and drying for 10h in a 50 ℃ environment to obtain the surface modified conductive carbon black;
Placing PVDF in NMP for stirring at a proper rotating speed, and ensuring that PVDF is uniformly dispersed in NMP;
And adding the anode active material, the modified conductive carbon black and the carbon nano tube into the PVDF glue solution in proper sequence, stirring at proper rotation speed for proper time, coating by a coating machine, baking at proper temperature, rolling, cutting and preparing the anode plate.
Example 3
Dispersing conductive carbon black in 8wt% hydrogen peroxide, wherein the mass ratio of the conductive carbon black to the hydrogen peroxide is 1:7, stirring in a water bath at the stirring speed of 10r/s after stirring and dispersing the suspension, and the water bath temperature is 40 ℃ and the water bath time is 3min;
Filtering the solid-liquid mixture with proper filter paper, washing with clean water for 2 times, and drying at 50 ℃ for 10 hours to obtain conductive carbon black with alcoholized surface;
Dispersing the alcoholized carbon black in an ethanol solution, and placing the ethanol solution in an ultrasonic water tank for ultrasonic dispersion for 5min, wherein the mass ratio of ethanol to alcoholized carbon black is 1:5, a step of; adding gamma-methacryloxypropyl trimethoxy silane into the ultrasonic solution, wherein the mass ratio of the gamma-methacryloxypropyl trimethoxy silane to the carbon black is 1:50, adding a proper amount of distilled water at the same time, stirring for 1min at a slow speed, and standing for 30min to ensure that the gamma-aminopropyl triethoxysilane is fully hydrolyzed;
Carrying out water bath on the mixed solution, wherein the water bath temperature is 80 ℃, the water bath is carried out for 10min, cooling to room temperature, carrying out suction filtration, cleaning with clean water, and drying for 10h in a 50 ℃ environment to obtain the surface modified conductive carbon black;
Placing PVDF in NMP for stirring at a proper rotating speed, and ensuring that PVDF is uniformly dispersed in NMP;
And adding the anode active material, the modified conductive carbon black and the carbon nano tube into the PVDF glue solution in proper sequence, stirring at proper rotation speed for proper time, coating by a coating machine, baking at proper temperature, rolling, cutting and preparing the anode plate.
Example 4
(1) Dispersing conductive carbon black in 60wt% concentrated sulfuric acid, wherein the mass ratio of the conductive carbon black to the concentrated sulfuric acid is 1:8, stirring in a water bath at the stirring speed of 10r/s after stirring and dispersing to obtain suspension, and the water bath temperature is 40 ℃ and the water bath time is 1min;
(2) Filtering the solid-liquid mixture with proper filter paper, alternately flushing with clean water and ethanol for 2 times, and drying at 50 ℃ for 10 hours to obtain conductive carbon black with alcoholized surface;
(3) Dispersing the alcoholized carbon black in an ethanol solution, and placing the ethanol solution in an ultrasonic water tank for ultrasonic dispersion for 5min, wherein the mass ratio of ethanol to alcoholized carbon black is 1:5, a step of; adding gamma-aminopropyl triethoxysilane into the ultrasonic solution, wherein the mass ratio of the gamma-aminopropyl triethoxysilane to the carbon black is 1:50, adding a proper amount of distilled water at the same time, stirring slowly for 1min, and standing for 30min to ensure that the gamma-aminopropyl triethoxysilane is fully hydrolyzed;
(4) Carrying out water bath on the mixed solution, wherein the water bath temperature is 80 ℃, the water bath is carried out for 10min, cooling to room temperature, carrying out suction filtration, cleaning with clean water, and drying for 10h in a 50 ℃ environment to obtain the surface modified conductive carbon black;
(5) Placing PVDF in NMP for stirring at a proper rotating speed, and ensuring that PVDF is uniformly dispersed in NMP;
(6) And adding the anode active material, the modified conductive carbon black and the carbon nano tube into the PVDF glue solution in proper sequence, stirring at proper rotation speed for proper time, coating by a coating machine, baking at proper temperature, rolling, cutting and preparing the anode plate.
Example 5
(1) Dispersing conductive carbon black in 60wt% concentrated nitric acid, wherein the mass ratio of the conductive carbon black to the concentrated nitric acid is 1:8, stirring in a water bath at the stirring speed of 10r/s and the water bath temperature of 40 ℃ for 1min after stirring and dispersing to obtain suspension;
(2) Filtering the solid-liquid mixture with proper filter paper, alternately flushing with clean water and ethanol for 2 times, and drying at 50 ℃ for 10 hours to obtain conductive carbon black with alcoholized surface;
(3) Dispersing the alcoholized carbon black in an ethanol solution, and placing the ethanol solution in an ultrasonic water tank for ultrasonic dispersion for 5min, wherein the mass ratio of ethanol to alcoholized carbon black is 1:5, a step of; adding gamma-aminopropyl triethoxysilane into the ultrasonic solution, wherein the mass ratio of the gamma-aminopropyl triethoxysilane to the carbon black is 1:50, adding a proper amount of distilled water at the same time, stirring slowly for 1min, and standing for 30min to ensure that the gamma-aminopropyl triethoxysilane is fully hydrolyzed;
(4) Carrying out water bath on the mixed solution, wherein the water bath temperature is 80 ℃, the water bath is carried out for 10min, cooling to room temperature, carrying out suction filtration, cleaning with clean water, and drying for 10h in a 50 ℃ environment to obtain the surface modified conductive carbon black;
(5) Placing PVDF in NMP for stirring at a proper rotating speed, and ensuring that PVDF is uniformly dispersed in NMP;
(6) And adding the anode active material, the modified conductive carbon black and the carbon nano tube into the PVDF glue solution in proper sequence, stirring at proper rotation speed for proper time, coating by a coating machine, baking at proper temperature, rolling, cutting and preparing the anode plate.
Example 6
(1) Dispersing conductive carbon black in absolute ethyl alcohol, wherein the mass ratio of the conductive carbon black to the absolute ethyl alcohol is 1:10, stirring in a water bath at the stirring speed of 10r/s after stirring and dispersing to obtain suspension, and the water bath temperature is 80 ℃ and the water bath time is 30min;
(2) Filtering the solid-liquid mixture with proper filter paper, washing with clean water for 2 times, and drying at 50 ℃ for 10 hours to obtain conductive carbon black with alcoholized surface;
(3) Dispersing the alcoholized carbon black in an ethanol solution, and placing the ethanol solution in an ultrasonic water tank for ultrasonic dispersion for 5min, wherein the mass ratio of ethanol to alcoholized carbon black is 1:5, a step of; adding gamma-aminopropyl triethoxysilane into the ultrasonic solution, wherein the mass ratio of the gamma-aminopropyl triethoxysilane to the carbon black is 1:50, adding a proper amount of distilled water at the same time, stirring slowly for 1min, and standing for 30min to ensure that the gamma-aminopropyl triethoxysilane is fully hydrolyzed;
(4) Carrying out water bath on the mixed solution, wherein the water bath temperature is 80 ℃, the water bath is carried out for 10min, cooling to room temperature, carrying out suction filtration, cleaning with clean water, and drying for 10h in a 50 ℃ environment to obtain the surface modified conductive carbon black;
(5) Placing PVDF in NMP for stirring at a proper rotating speed, and ensuring that PVDF is uniformly dispersed in NMP;
(6) And adding the anode active material, the modified conductive carbon black and the carbon nano tube into the PVDF glue solution in proper sequence, stirring at proper rotation speed for proper time, coating by a coating machine, baking at proper temperature, rolling and cutting to prepare the anode plate.
As shown in fig. 2, conductive carbon black (SP) agglomerates without surface modification; as shown in fig. 4, the conductive carbon black (SP) surface-modified in the embodiment of the present invention is uniformly dispersed.
As shown in fig. 5, the energy retention rate of the conductive carbon black (SP) subjected to surface modification in the embodiment of the present invention is far higher than that of the conductive carbon black (SP) not subjected to surface modification in the cycle process; as shown in fig. 6, the increase rate of the ac internal resistance (ACR) of the battery of the conductive carbon black (SP) surface-modified according to the embodiment of the present invention was reduced. It can be seen from fig. 3, 5 and 6 that the conductive carbon black (SP) with surface modification in the embodiment of the present invention improves the fatigue of the binder, effectively relieves the fatigue of the binder in the aging process of the battery, and ensures the continuity of the electronic path, effectively reduces the internal resistance growth rate of the positive plate, and further improves the overall performance of the battery.
It should be noted that, the limitation of each step in the present solution is not to be considered as limiting the sequence of steps on the premise of not affecting the implementation of the specific solution, and the steps written in the previous step may be executed before, or executed after, or even executed simultaneously, so long as the implementation of the present solution is possible, all the steps should be considered as falling within the protection scope of the present invention.
The above description of the invention in connection with specific alternative embodiments is further detailed and it is not intended that the invention be limited to the specific embodiments disclosed. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.

Claims (2)

1. The positive plate is characterized by comprising modified conductive carbon black and polyvinylidene fluoride; the modified conductive carbon black is prepared by a conductive carbon black modification method, and the conductive carbon black modification method comprises the following steps:
Dispersing conductive carbon black in an alcoholizing agent, stirring and dispersing the conductive carbon black, and then carrying out water bath, wherein the water bath temperature of the alcoholizing agent is 35-50 ℃ and the water bath time is 1-10 min so as to alcoholize the conductive carbon black;
separating out the conductive carbon black in the alcoholizing agent to obtain the conductive carbon black with hydroxyl groups on the surface after alcoholizing;
Dispersing alcoholized conductive carbon black in ethanol solution, adding a surface modifier, and carrying out water bath, wherein the water bath temperature of the ethanol solution is 70-85 ℃ and the water bath time is 8-13 min; the hydroxyl groups of the conductive carbon black react with the hydroxyl groups of the hydrolyzed surface modifier to form ether bonds, so that the surface modifier is hydrolyzed and then coated and grafted on the surface of the conductive carbon black; adding water into the ethanol solution to promote the surface modifier to be fully hydrolyzed;
Separating out conductive carbon black in the ethanol solution to obtain surface-modified conductive carbon black, wherein the modified conductive carbon black can perform a chemical bonding function with polyvinylidene fluoride (PVDF);
The surface modifier is gamma-aminopropyl triethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane or gamma-methacryloxypropyl trimethoxysilane;
the alcoholizing agent is hydrogen peroxide, concentrated sulfuric acid, concentrated nitric acid, alcohols or weak acid.
2. A battery comprising the positive electrode sheet according to claim 1.
CN202210681592.2A 2022-06-16 2022-06-16 Conductive carbon black modification method, modified conductive carbon black, positive plate and battery Active CN114989642B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210681592.2A CN114989642B (en) 2022-06-16 2022-06-16 Conductive carbon black modification method, modified conductive carbon black, positive plate and battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210681592.2A CN114989642B (en) 2022-06-16 2022-06-16 Conductive carbon black modification method, modified conductive carbon black, positive plate and battery

Publications (2)

Publication Number Publication Date
CN114989642A CN114989642A (en) 2022-09-02
CN114989642B true CN114989642B (en) 2024-05-17

Family

ID=83035585

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210681592.2A Active CN114989642B (en) 2022-06-16 2022-06-16 Conductive carbon black modification method, modified conductive carbon black, positive plate and battery

Country Status (1)

Country Link
CN (1) CN114989642B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116535880A (en) * 2023-05-06 2023-08-04 沈阳航空航天大学 Carbon black hydrophobic modification method for ABS resin

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008195837A (en) * 2007-02-14 2008-08-28 Daito Kasei Kogyo Kk Surface treated carbon black and its manufacturing method, water dispersion formed by dispersing same, and cosmetic, ink and coating containing the dispersion
CN102532669A (en) * 2012-01-12 2012-07-04 上海交通大学 High polymer-based graphene composite material with positive resistance temperature coefficient and preparation method
JP2014193986A (en) * 2013-02-27 2014-10-09 Toyo Ink Sc Holdings Co Ltd Carbon black dispersion and use thereof
CN106380630A (en) * 2016-08-29 2017-02-08 北京化工大学 Preparation method and application of chemical-bonded thermally-conductive insulation composite filling material
JP2017135062A (en) * 2016-01-29 2017-08-03 東洋インキＳｃホールディングス株式会社 Method for manufacturing carbon black dispersion for lithium ion secondary battery
CN107033632A (en) * 2017-04-20 2017-08-11 安徽春辉仪表线缆集团有限公司 A kind of hyper-branched polyester functional graft carbon black conductive filler and preparation method thereof
CN112436146A (en) * 2020-11-20 2021-03-02 安徽南都华拓新能源科技有限公司 Lithium battery positive electrode material, preparation method and lithium battery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI581484B (en) * 2014-12-31 2017-05-01 財團法人工業技術研究院 A battery electrode paste composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008195837A (en) * 2007-02-14 2008-08-28 Daito Kasei Kogyo Kk Surface treated carbon black and its manufacturing method, water dispersion formed by dispersing same, and cosmetic, ink and coating containing the dispersion
CN102532669A (en) * 2012-01-12 2012-07-04 上海交通大学 High polymer-based graphene composite material with positive resistance temperature coefficient and preparation method
JP2014193986A (en) * 2013-02-27 2014-10-09 Toyo Ink Sc Holdings Co Ltd Carbon black dispersion and use thereof
JP2017135062A (en) * 2016-01-29 2017-08-03 東洋インキＳｃホールディングス株式会社 Method for manufacturing carbon black dispersion for lithium ion secondary battery
CN106380630A (en) * 2016-08-29 2017-02-08 北京化工大学 Preparation method and application of chemical-bonded thermally-conductive insulation composite filling material
CN107033632A (en) * 2017-04-20 2017-08-11 安徽春辉仪表线缆集团有限公司 A kind of hyper-branched polyester functional graft carbon black conductive filler and preparation method thereof
CN112436146A (en) * 2020-11-20 2021-03-02 安徽南都华拓新能源科技有限公司 Lithium battery positive electrode material, preparation method and lithium battery

Also Published As

Publication number Publication date
CN114989642A (en) 2022-09-02

Similar Documents

Publication Publication Date Title
CN104495935B (en) A kind of strip preparation method of molybdenum disulfide nano sheet layer
CN103474666A (en) Preparation method for negative electrode active material of lithium ion battery
CN111600000B (en) Carbon nanotube graphene/silicon carbon composite material, and preparation method and application thereof
CN107915853A (en) A kind of nano-cellulose/graphene composite and flexible film and preparation method and application
CN106328913A (en) Surface modification method for silicon negative electrode material of lithium ion battery, silicon negative electrode material and application
CN114989642B (en) Conductive carbon black modification method, modified conductive carbon black, positive plate and battery
CN114079054B (en) Lithium battery negative electrode material and preparation method thereof
TWI686001B (en) Polymer-modified silicon-carbon composite and use thereof
CN105226253B (en) A kind of silicon nanoparticle-graphite flake-carbon nano tube compound material and the preparation method and application thereof
CN109103440B (en) Lithium ion battery cathode material, preparation method and lithium ion battery
CN107959027A (en) Silicon-based negative electrode binder of lithium ion battery and preparation method of negative plate containing binder
CN113991109B (en) Sodium manganese fluorophosphate/titanium carbide lamellar-carbon quantum dot composite material and preparation method and application thereof
CN111668449A (en) Silicon composite negative electrode material for lithium ion battery and preparation method thereof
WO2023020042A1 (en) Silicon-carbon composite negative electrode material, preparation method therefor and application thereof
CN113782857A (en) Method for repairing and regenerating anode material of waste lithium iron phosphate battery and application
CN114725322B (en) Preparation method of silicon-titanium dioxide-graphene flexible self-supporting electrode
CN115939344A (en) Silane coupling agent coated modified sodium-electricity positive electrode material, preparation method and application
CN118448618A (en) Graphite-silicon-amorphous carbon composite negative electrode material and preparation method thereof
CN114181547A (en) Preparation method of nano carbon black
CN110707290B (en) Preparation method of flexible lithium ion battery negative electrode with sandwich-like structure
CN114497516A (en) Yolk-shell type carbon-coated silicon composite negative electrode material and preparation method thereof
CN111682186B (en) Silicon-carbon composite material, preparation method and application thereof
CN111740090B (en) Synthetic method for improving conductivity of silicon-based negative electrode material
CN116715226A (en) Modified carbon nanotube, preparation method, positive plate and lithium ion battery
CN112332025A (en) Diaphragm for lithium-sulfur battery and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant