CN109037685A - A kind of preparation method of conductive agent - Google Patents
A kind of preparation method of conductive agent Download PDFInfo
- Publication number
- CN109037685A CN109037685A CN201810727172.7A CN201810727172A CN109037685A CN 109037685 A CN109037685 A CN 109037685A CN 201810727172 A CN201810727172 A CN 201810727172A CN 109037685 A CN109037685 A CN 109037685A
- Authority
- CN
- China
- Prior art keywords
- added
- mass ratio
- stirred
- conductive agent
- obtains
- 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.)
- Withdrawn
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of conductive agent, belong to technical field of energy material.Acid oxidant is made with cobalt sulfate, hydrogenperoxide steam generator, Ammonium Molybdate Tetrahydrate in the present invention, plays oxidation；Based on N-phenylglycine, acid oxidant obtained is added, after N- substitution is carboxy-modified, so that conductive agent has preferable stability in aqueous solution and electrochemical process；Carbon nanotube is added, thiosemicarbazide is passed through nitrogen, improve the conductivity of conductive agent, S is fully participated in electrode reaction, and then the cycle performance of electrode is significantly improved, sodium alginate is introduced, volume expansion can be effectively alleviated, shorten electronics and ion transmission path, so that expanding possibility in conducting process reduces.The present invention is solved for the problem that the conductive agent electric conductivity added in current lithium battery is bad, and volume expansion easily occurs during charge and discharge cycles.
Description
Technical field
The invention belongs to technical field of energy material, and in particular to a kind of preparation method of conductive agent.
Background technique
From lithium ion battery working principle it is found that the charge and discharge process of battery, needs the common participation of lithium ion and electronics,
Therefore, the electrode of lithium ion battery must be the mixture of ion and electronics, and electrode reaction also can only occur in electrolyte, conduction
Agent, active material interface.In lithium ion battery, cathode active material is mostly transition metal oxide or transition metal
Phosphate, belongs to semiconductor or insulator mostly, and electric conductivity is very poor, it is necessary to conductive agent be added to improve electric conductivity；Anode graphite
The electric conductivity of material is slightly good, but in multiple charge and discharge process, the expansion and contraction of graphite material, so that between graphite particle
Contact reduce, gap increase, some even be detached from collector, become dead active material, be no longer participate in electrode reaction, so
It is also required to that stabilization of the conductive agent to be maintained at the electrode material electric conductivity during circulating battery is added.Existing common conductive agent
There are carbon black, electrically conductive graphite, carbon nanotube and carbon nano-fiber etc..In existing common conductive agent, electrically conductive polyaniline has price
Cheap, the advantages that synthesis technology is simple, anticorrosion ability is excellent, it is considered to be most have actual application prospect conducting polymer it
One.But electrically conductive polyaniline haves the shortcomings that electric conductivity is bad, to limit its heavy industrialization application.Research later
It was found that electrically conductive polyaniline and the inorganic nano material compound resulting polyaniline/inorganic nano composite material on nanoscale, no
The electric conductivity of polyaniline can only be improved, but also can have several functions, so as to cause extensive concern.But it is poly-
It is easily settled when aniline/inorganic nano composite material is as coating, the service life of coating is influenced, and in charge and discharge cycles process
In will lead to 300% volume expansion, the dusting and peeling of active material are caused, so as to cause the rapid decaying of capacity.
Summary of the invention
The technical problems to be solved by the invention: it is bad for the conductive agent electric conductivity added in current lithium battery, and
The problem of volume expansion easily occurs during charge and discharge cycles provides a kind of preparation method of conductive agent.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of preparation method of conductive agent includes the following steps:
(1) take cobalt sulfate 1 ~ 3:15 in mass ratio ~ 18 be added deionized water mixing, add cobalt sulfate quality 40 ~
60% hydrogenperoxide steam generator, obtains mixed liquor, takes mixed liquor 10 ~ 15:12 ~ 18 to be in mass ratio added dropwise to Ammonium Molybdate Tetrahydrate water-soluble
It in liquid, is stirred, rotary evaporation, obtains rotary evaporation object, take rotary evaporation object 2 ~ 5:10 in mass ratio ~ 13 that distilled water is added,
It stands, filters, take suction filtration slag, it is spare；
(2) take N-phenylglycine 1 ~ 3:4 in mass ratio ~ 6:4 ~ 6 that acetonitrile, water is added, ultrasound obtains ultrasonic object, takes 3,4- ethylene
Kayexalate is added in dioxy thiophene 1 ~ 3:3 in mass ratio ~ 5, is stirred, obtains mixture, takes mixture in mass ratio 1
Deionized water is added in ~ 3:3 ~ 7, adds the graphene of mixture quality 0.5 ~ 1%, and ultrasound obtains ultrasonic liquid；
(3) the suction filtration slag 1 ~ 3:10 in mass ratio ~ 13 for taking step (1) spare is added the hydrochloric acid that mass fraction is 20% and is stirred,
Mixture must be stirred, takes stirring mixture 8 ~ 15:4 in mass ratio ~ 7:2 ~ 4 that ultrasonic object, ultrasonic liquid is added dropwise, it is mixed in 3 ~ 7 DEG C of stirrings
Conjunction 18 ~ for 24 hours, filtering takes filter residue through deionized water, ethanol washing, and drying obtains dried object, and taking dried object that concentration is added is 1mol/
The ammonium hydroxide of L, is stirred, and filtering takes filter residue a, dry, obtains dried object a；
(4) take thiosemicarbazide 1 ~ 3:5 in mass ratio ~ 9 that carbon nanotubes is added, grinding obtains abrasive material, takes abrasive material that quality is added
The nitric acid mixing that sulfuric acid that score is 98%, mass fraction are 69%, ultrasound obtain ultrasonic object a, take ultrasonic object a 1 ~ 3:9 in mass ratio
~ 12 are added deionized water, adjust pH to 7 ~ 7.2, dry, obtain dried object b, dried object b is taken to be passed through nitrogen, keep the temperature, be cooled to room
Temperature obtains cooled material；
(5) take sodium alginate 1 ~ 3:30 in mass ratio ~ 50 that distilled water is added, 40 ~ 50min of magnetic agitation obtains stirring mixture, takes
It stirs mixture 2 ~ 4:8 in mass ratio ~ 15:1 ~ 3 and cooled material, lauryl sodium sulfate is added, be stirred 1 ~ 2h in 2 ~ 4 DEG C,
The ammonium persulfate for being stirred amount of substance 1 ~ 3% is added, 3 ~ 5min is stirred, is freeze-dried to get conductive agent.
Rotary evaporation object is stirred condition in the step (1) are as follows: be warming up to 95 ~ 100 DEG C be stirred 30 ~
40min, rotary evaporation.
The stirring condition of stirring mixture in the step (3) are as follows: be stirred 20 ~ 30min in 20 ~ 25 DEG C.
The mass ratio for the ammonium hydroxide that dried object and concentration are 1mol/L in the step (3) is 2 ~ 5:10 ~ 15.
The mass ratio for the nitric acid that abrasive material, mass fraction are 98% in the step (4) sulfuric acid, mass fraction are 69% is
1 ~ 4:3 ~ 5:8 ~ 12.
Dried object b is passed through the heat-retaining condition of nitrogen in the step (4) are as follows: in 600 ~ 700 DEG C of 10 ~ 12h of heat preservation.
The mass ratio of mixture, cooled material, lauryl sodium sulfate is stirred in the step (5) are as follows: 2 ~ 4:8 ~ 15:1 ~ 3.
The present invention is compared with other methods, and advantageous effects are:
(1) acid oxidant is made with cobalt sulfate, hydrogenperoxide steam generator, Ammonium Molybdate Tetrahydrate in the present invention, plays oxidation and makees
With after oxidant further progress doped hydrochloride obtained, dielectric constant and dielectric loss are improved, and doped hydrochloride is added
Afterwards, the dielectric constant of the polyaniline compound substance obtained is improved, this is because increasing after Bronsted acid enters product molecule chain
Caused by the polarity of molecule；
(2) acid oxidant obtained is added based on N-phenylglycine in the present invention, main to conduction using chemical oxidising polymerisation
Body is modified, using the hydrophily carboxyl being introduced into acid oxidant on polymer molecular chain, to obtain a kind of solubility
Good, the stronger matrix object of electric conductivity, after N- substitution is carboxy-modified, polymerization oxidation current potential is mobile to low potential direction, gathers
After the hydrogen atom on nitrogen-atoms in aniline category matter strand is replaced second carboxylic group, strand has preferably steady
It is qualitative and be not easy to be oxidized, therefore conductive agent has preferable stability in aqueous solution and electrochemical process；
(3) present invention during oxidation polymerization using graphene as template in-situ polymerization matrix object when, formation polymer head
First be adsorbed on the surface of graphene, be then added synthesis oxidant compounded with hydrochloric acid shape in the presence of in-situ polymerization, stone occurs
Electrically conductive layer is formd on black alkene surface, 3,4-rthylene dioxythiophene nano particle is evenly dispersed on the surface of graphene, 3,4- second
Alkene dioxy thiophene, polystyrolsulfon acid nano wire bridge between graphene microchip, have constructed a large amount of multidimensional conductive networks, favorably
In the transmission of carrier, dispersibility of the graphene microchip in polyaniline matrix was not only improved, but also promote graphene microchip and polyphenyl
Good combination between amido body reduces its contact resistance with matrix, to improve the conductivity of conductive agent；
(4) carbon nanotube is added in the present invention, because it with unique nanostructure, three-dimensional space net structure and excellent is led
Electrical property is added thiosemicarbazide, is passed through nitrogen, so that N atom is doped into the net of carbon nanotube in the form of " graphitic N "
The conductivity that conductive agent is improved when shape structure, participates in S fully in electrode reaction, and then significantly improves electricity
The cycle performance of pole introduces sodium alginate, and sodium alginate molecule has many carboxyls and hydroxyl, can be with conductive agent polymer shape
At hydrogen bond to constitute three-dimensional interpenetrating polymer network, which has good self supporting structure, and mechanical strength is preferable, so that conductive
Agent has bigger specific surface area and higher porosity, can effectively alleviate volume expansion, shortens electronics and ion transmission
Path, so that expanding possibility in conducting process reduces.
Specific embodiment
A kind of preparation method of conductive agent, includes the following steps:
(1) take cobalt sulfate 1 ~ 3:15 in mass ratio ~ 18 be added deionized water mixing, add cobalt sulfate quality 40 ~
The hydrogenperoxide steam generator that 60% mass fraction is 30%, obtains mixed liquor, takes mixed liquor 10 ~ 15:12 ~ 18 to be in mass ratio added dropwise to dense
Degree is to be warming up to 95 ~ 100 DEG C in the Ammonium Molybdate Tetrahydrate aqueous solution of 0.09mol/L and be stirred 30 ~ 40min, rotary evaporation,
Rotary evaporation object is obtained, takes rotary evaporation object 2 ~ 5:10 in mass ratio ~ 13 that distilled water is added, in 75 ~ 80 DEG C of 20 ~ 30min of standing, is taken out
Filter, takes suction filtration slag, spare；
(2) take N-phenylglycine 1 ~ 3:4 in mass ratio ~ 6:4 ~ 6 that acetonitrile, water is added, 3 ~ 6min of ultrasound obtains ultrasonic object, takes 3,
Kayexalate is added in 4- ethene dioxythiophene 1 ~ 3:3 in mass ratio ~ 5, is stirred 20 ~ 30min, obtains mixture, takes
Deionized water is added in mixture 1 ~ 3:3 in mass ratio ~ 7, adds the graphene of mixture quality 0.5 ~ 1%, and ultrasound 10 ~
15min obtains ultrasonic liquid；
(3) hydrochloric acid that mass fraction is 20% is added in the suction filtration slag 1 ~ 3:10 in mass ratio ~ 13 for taking step (1) spare, in 20 ~ 25
DEG C it is stirred 20 ~ 30min, obtains stirring mixture, takes stirring mixture 8 ~ 15:4 in mass ratio ~ 7:2 ~ 4 that ultrasonic object, super is added dropwise
Sound liquid, is stirred 18 in 3 ~ 7 DEG C ~ for 24 hours, filtering, takes filter residue through deionized water, ethanol washing, dry, obtains dried object, takes dry
The ammonium hydroxide that concentration is 1mol/L is added in dry object 2 ~ 5:10 in mass ratio ~ 15, is stirred 6 ~ 9h, filters, takes filter residue a, dry, obtains
Dried object a；
(4) it takes thiosemicarbazide 1 ~ 3:5 in mass ratio ~ 9 that carbon nanotubes is added, grinds 50 ~ 60min, obtain abrasive material, take abrasive material
The nitric acid mixing that the sulfuric acid that mass fraction is 98% is added in 1 ~ 4:3 in mass ratio ~ 5:8 ~ 12, mass fraction is 69%, ultrasound 18 ~
For 24 hours, ultrasonic object a is obtained, takes ultrasonic object a 1 ~ 3:9 in mass ratio ~ 12 that deionized water is added, adjusts pH to 7 ~ 7.2, it is dry, obtain drying
Object b takes dried object b to be passed through nitrogen, in 600 ~ 700 DEG C of 10 ~ 12h of heat preservation, is cooled to room temperature, obtains cooled material；
(5) take sodium alginate 1 ~ 3:30 in mass ratio ~ 50 that distilled water is added, 40 ~ 50min of magnetic agitation obtains stirring mixture, takes
It stirs mixture 2 ~ 4:8 in mass ratio ~ 15:1 ~ 3 and cooled material, lauryl sodium sulfate is added, be stirred 1 ~ 2h in 2 ~ 4 DEG C,
The ammonium persulfate for being stirred amount of substance 1 ~ 3% is added, 3 ~ 5min is stirred, is freeze-dried to get conductive agent.
Embodiment 1
A kind of preparation method of conductive agent, includes the following steps:
(1) it takes cobalt sulfate 1:15 in mass ratio that deionized water mixing is added, adds the quality of cobalt sulfate quality 40%
The hydrogenperoxide steam generator that score is 30%, obtains mixed liquor, and taking mixed liquor 10:12 to be in mass ratio added dropwise to concentration is 0.09mol/L's
In Ammonium Molybdate Tetrahydrate aqueous solution, it is warming up to 95 DEG C and is stirred 30min, rotary evaporation obtains rotary evaporation object, takes rotary evaporation
Distilled water is added in object 2:10 in mass ratio, in 75 DEG C of standing 20min, filters, takes suction filtration slag, spare；
(2) take N-phenylglycine 1:4:4 in mass ratio that acetonitrile, water is added, ultrasonic 3min obtains ultrasonic object, takes 3,4- ethylene two
Kayexalate is added in oxygen thiophene 1:3 in mass ratio, is stirred 20min, obtains mixture, takes mixture in mass ratio 1:
3 are added deionized water, add the graphene of mixture quality 0.5%, ultrasonic 10min obtains ultrasonic liquid；
(3) hydrochloric acid that mass fraction is 20% is added in the suction filtration slag 1:10 in mass ratio for taking step (1) spare, mixed in 20 DEG C of stirrings
20min is closed, stirring mixture is obtained, takes stirring mixture 8:4:2 in mass ratio that ultrasonic object, ultrasonic liquid is added dropwise, is stirred in 3 DEG C
18h, filtering take filter residue through deionized water, ethanol washing, and drying obtains dried object, take dried object 2:10 in mass ratio that concentration is added
For the ammonium hydroxide of 1mol/L, it is stirred 6h, filters, takes filter residue a, it is dry, obtain dried object a；
(4) it takes thiosemicarbazide 1:5 in mass ratio that carbon nanotubes is added, grinds 50min, obtain abrasive material, take abrasive material by quality
The nitric acid mixing that sulfuric acid, mass fraction that mass fraction is 98% are 69% is added than 1:3:8, ultrasonic 18h obtains ultrasonic object a, take super
Deionized water is added in sound object a 1:9 in mass ratio, adjusts pH to 7, dry, obtains dried object b, takes dried object b to be passed through nitrogen, in 600
DEG C heat preservation 10h, be cooled to room temperature, obtain cooled material；
(5) take sodium alginate 1:30 in mass ratio that distilled water is added, magnetic agitation 40min obtains stirring mixture, takes and be stirred
Cooled material, lauryl sodium sulfate is added in object 2:8:1 in mass ratio, is stirred 1h in 2 DEG C, adds and be stirred amount of substance
1% ammonium persulfate is stirred 3min, is freeze-dried to get conductive agent.
Embodiment 2
A kind of preparation method of conductive agent, includes the following steps:
(1) it takes cobalt sulfate 2:17 in mass ratio that deionized water mixing is added, adds the quality of cobalt sulfate quality 50%
The hydrogenperoxide steam generator that score is 30%, obtains mixed liquor, and taking mixed liquor 13:15 to be in mass ratio added dropwise to concentration is 0.09mol/L's
In Ammonium Molybdate Tetrahydrate aqueous solution, it is warming up to 98 DEG C and is stirred 35min, rotary evaporation obtains rotary evaporation object, takes rotary evaporation
Distilled water is added in object 4:12 in mass ratio, in 78 DEG C of standing 25min, filters, takes suction filtration slag, spare；
(2) take N-phenylglycine 2:5:5 in mass ratio that acetonitrile, water is added, ultrasonic 5min obtains ultrasonic object, takes 3,4- ethylene two
Kayexalate is added in oxygen thiophene 2:4 in mass ratio, is stirred 25min, obtains mixture, takes mixture in mass ratio 2:
5 are added deionized water, add the graphene of mixture quality 0.8%, ultrasonic 13min obtains ultrasonic liquid；
(3) hydrochloric acid that mass fraction is 20% is added in the suction filtration slag 2:12 in mass ratio for taking step (1) spare, mixed in 23 DEG C of stirrings
25min is closed, stirring mixture is obtained, takes stirring mixture 12:6:3 in mass ratio that ultrasonic object, ultrasonic liquid is added dropwise, it is mixed in 5 DEG C of stirrings
21h is closed, filtering takes filter residue through deionized water, ethanol washing, and drying obtains dried object, takes dried object 4:13 to be in mass ratio added dense
Degree is the ammonium hydroxide of 1mol/L, is stirred 8h, filters, takes filter residue a, dry, obtains dried object a；
(4) it takes thiosemicarbazide 2:7 in mass ratio that carbon nanotubes is added, grinds 55min, obtain abrasive material, take abrasive material by quality
The nitric acid mixing that sulfuric acid, mass fraction that mass fraction is 98% are 69% is added than 3:4:10, ultrasonic 21h obtains ultrasonic object a, take
Deionized water is added in ultrasonic object a 2:11 in mass ratio, adjusts pH to 7.1, dry, obtains dried object b, dried object b is taken to be passed through nitrogen,
In 650 DEG C of heat preservation 11h, it is cooled to room temperature, obtains cooled material；
(5) take sodium alginate 2:40 in mass ratio that distilled water is added, magnetic agitation 45min obtains stirring mixture, takes and be stirred
Cooled material, lauryl sodium sulfate is added in object 3:12:2 in mass ratio, is stirred 1.5h in 3 DEG C, adds stirring mixture
The ammonium persulfate of quality 2% is stirred 4min, is freeze-dried to get conductive agent.
Embodiment 3
A kind of preparation method of conductive agent, includes the following steps:
(1) take cobalt sulfate 1 ~ 3:15 in mass ratio ~ 18 be added deionized water mixing, add cobalt sulfate quality 40 ~
The hydrogenperoxide steam generator that 60% mass fraction is 30%, obtains mixed liquor, takes mixed liquor 10 ~ 15:12 ~ 18 to be in mass ratio added dropwise to dense
Degree is to be warming up to 95 ~ 100 DEG C in the Ammonium Molybdate Tetrahydrate aqueous solution of 0.09mol/L and be stirred 30 ~ 40min, rotary evaporation,
Rotary evaporation object is obtained, takes rotary evaporation object 2 ~ 5:10 in mass ratio ~ 13 that distilled water is added, in 75 ~ 80 DEG C of 20 ~ 30min of standing, is taken out
Filter, takes suction filtration slag, spare；
(2) take N-phenylglycine 1 ~ 3:4 in mass ratio ~ 6:4 ~ 6 that acetonitrile, water is added, 3 ~ 6min of ultrasound obtains ultrasonic object, takes 3,
Kayexalate is added in 4- ethene dioxythiophene 1 ~ 3:3 in mass ratio ~ 5, is stirred 20 ~ 30min, obtains mixture, takes
Deionized water is added in mixture 1 ~ 3:3 in mass ratio ~ 7, adds the graphene of mixture quality 0.5 ~ 1%, and ultrasound 10 ~
15min obtains ultrasonic liquid；
(3) hydrochloric acid that mass fraction is 20% is added in the suction filtration slag 1 ~ 3:10 in mass ratio ~ 13 for taking step (1) spare, in 20 ~ 25
DEG C it is stirred 20 ~ 30min, obtains stirring mixture, takes stirring mixture 8 ~ 15:4 in mass ratio ~ 7:2 ~ 4 that ultrasonic object, super is added dropwise
Sound liquid, is stirred 18 in 3 ~ 7 DEG C ~ for 24 hours, filtering, takes filter residue through deionized water, ethanol washing, dry, obtains dried object, takes dry
The ammonium hydroxide that concentration is 1mol/L is added in dry object 2 ~ 5:10 in mass ratio ~ 15, is stirred 6 ~ 9h, filters, takes filter residue a, dry, obtains
Dried object a；
(4) it takes thiosemicarbazide 1 ~ 3:5 in mass ratio ~ 9 that carbon nanotubes is added, grinds 50 ~ 60min, obtain abrasive material, take abrasive material
The nitric acid mixing that the sulfuric acid that mass fraction is 98% is added in 1 ~ 4:3 in mass ratio ~ 5:8 ~ 12, mass fraction is 69%, ultrasound 18 ~
For 24 hours, ultrasonic object a is obtained, takes ultrasonic object a 1 ~ 3:9 in mass ratio ~ 12 that deionized water is added, adjusts pH to 7 ~ 7.2, it is dry, obtain drying
Object b takes dried object b to be passed through nitrogen, in 600 ~ 700 DEG C of 10 ~ 12h of heat preservation, is cooled to room temperature, obtains cooled material；
(5) take sodium alginate 1 ~ 3:30 in mass ratio ~ 50 that distilled water is added, 40 ~ 50min of magnetic agitation obtains stirring mixture, takes
It stirs mixture 2 ~ 4:8 in mass ratio ~ 15:1 ~ 3 and cooled material, lauryl sodium sulfate is added, be stirred 1 ~ 2h in 2 ~ 4 DEG C,
The ammonium persulfate for being stirred amount of substance 1 ~ 3% is added, 3 ~ 5min is stirred, is freeze-dried to get conductive agent.
Comparative example: the conductive agent of Yixing City company production.
Conductive agent prepared by embodiment 1,2,3 and comparative example is applied in lithium ion battery, lithium ion battery is carried out
Performance test, test result record such as table 1.
In conclusion as shown in Table 1, conductive agent prepared by the present invention conducts electricity very well, and battery is not easy to expand after recycling,
Battery capacity is big, is worth advocating energetically.
Claims (7)
1. a kind of preparation method of conductive agent, which is characterized in that the preparation method includes the following steps:
(1) take cobalt sulfate 1 ~ 3:15 in mass ratio ~ 18 be added deionized water mixing, add cobalt sulfate quality 40 ~
60% hydrogenperoxide steam generator, obtains mixed liquor, takes mixed liquor 10 ~ 15:12 ~ 18 to be in mass ratio added dropwise to Ammonium Molybdate Tetrahydrate water-soluble
It in liquid, is stirred, rotary evaporation, obtains rotary evaporation object, take rotary evaporation object 2 ~ 5:10 in mass ratio ~ 13 that distilled water is added,
It stands, filters, take suction filtration slag, it is spare；
(2) take N-phenylglycine 1 ~ 3:4 in mass ratio ~ 6:4 ~ 6 that acetonitrile, water is added, ultrasound obtains ultrasonic object, takes 3,4- ethylene
Kayexalate is added in dioxy thiophene 1 ~ 3:3 in mass ratio ~ 5, is stirred, obtains mixture, takes mixture in mass ratio 1
Deionized water is added in ~ 3:3 ~ 7, adds the graphene of mixture quality 0.5 ~ 1%, and ultrasound obtains ultrasonic liquid；
(3) the suction filtration slag 1 ~ 3:10 in mass ratio ~ 13 for taking step (1) spare is added the hydrochloric acid that mass fraction is 20% and is stirred,
Mixture must be stirred, takes stirring mixture 8 ~ 15:4 in mass ratio ~ 7:2 ~ 4 that ultrasonic object, ultrasonic liquid is added dropwise, it is mixed in 3 ~ 7 DEG C of stirrings
Conjunction 18 ~ for 24 hours, filtering takes filter residue through deionized water, ethanol washing, and drying obtains dried object, and taking dried object that concentration is added is 1mol/
The ammonium hydroxide of L, is stirred, and filtering takes filter residue a, dry, obtains dried object a；
(4) take thiosemicarbazide 1 ~ 3:5 in mass ratio ~ 9 that carbon nanotubes is added, grinding obtains abrasive material, takes abrasive material that quality is added
The nitric acid mixing that sulfuric acid that score is 98%, mass fraction are 69%, ultrasound obtain ultrasonic object a, take ultrasonic object a 1 ~ 3:9 in mass ratio
~ 12 are added deionized water, adjust pH to 7 ~ 7.2, dry, obtain dried object b, dried object b is taken to be passed through nitrogen, keep the temperature, be cooled to room
Temperature obtains cooled material；
(5) take sodium alginate 1 ~ 3:30 in mass ratio ~ 50 that distilled water is added, 40 ~ 50min of magnetic agitation obtains stirring mixture, takes
It stirs mixture 2 ~ 4:8 in mass ratio ~ 15:1 ~ 3 and cooled material, lauryl sodium sulfate is added, be stirred 1 ~ 2h in 2 ~ 4 DEG C,
The ammonium persulfate for being stirred amount of substance 1 ~ 3% is added, 3 ~ 5min is stirred, is freeze-dried to get conductive agent.
2. the preparation method of conductive agent according to claim 1, which is characterized in that rotary evaporation object in the step (1)
Be stirred condition are as follows: be warming up to 95 ~ 100 DEG C and be stirred 30 ~ 40min, rotary evaporation.
3. the preparation method of conductive agent according to claim 1, which is characterized in that stir mixture in the step (3)
Stirring condition are as follows: be stirred 20 ~ 30min in 20 ~ 25 DEG C.
4. the preparation method of conductive agent according to claim 1, which is characterized in that in the step (3) dried object with it is dense
The mass ratio for the ammonium hydroxide that degree is 1mol/L is 2 ~ 5:10 ~ 15.
5. the preparation method of conductive agent according to claim 1, which is characterized in that abrasive material, quality in the step (4)
The mass ratio for the nitric acid that sulfuric acid that score is 98%, mass fraction are 69% is 1 ~ 4:3 ~ 5:8 ~ 12.
6. the preparation method of conductive agent according to claim 1, which is characterized in that dried object b is passed through in the step (4)
The heat-retaining condition of nitrogen are as follows: in 600 ~ 700 DEG C of 10 ~ 12h of heat preservation.
7. the preparation method of conductive agent according to claim 1, which is characterized in that the middle stirring mixture of the step (5),
The mass ratio of cooled material, lauryl sodium sulfate are as follows: 2 ~ 4:8 ~ 15:1 ~ 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810727172.7A CN109037685A (en) | 2018-07-05 | 2018-07-05 | A kind of preparation method of conductive agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810727172.7A CN109037685A (en) | 2018-07-05 | 2018-07-05 | A kind of preparation method of conductive agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109037685A true CN109037685A (en) | 2018-12-18 |
Family
ID=65521811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810727172.7A Withdrawn CN109037685A (en) | 2018-07-05 | 2018-07-05 | A kind of preparation method of conductive agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109037685A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100055572A1 (en) * | 2006-05-04 | 2010-03-04 | Lg Chem, Ltd. | Electrochemical Energy Storage Device with High Capacity and High Power Using Conductive Polymer Composite |
| CN102921473A (en) * | 2012-09-28 | 2013-02-13 | 石河子大学 | Novel nitrogen-modified carbon catalyst carrier and preparation method and use thereof |
| CN103214671A (en) * | 2013-05-07 | 2013-07-24 | 华东交通大学 | Chemical oxidation preparation method for novel N-substituted carboxyl polyaniline |
| CN107394207A (en) * | 2017-06-27 | 2017-11-24 | 宁波墨西科技有限公司 | A kind of graphene composite conductive powder and preparation method thereof |
-
2018
- 2018-07-05 CN CN201810727172.7A patent/CN109037685A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100055572A1 (en) * | 2006-05-04 | 2010-03-04 | Lg Chem, Ltd. | Electrochemical Energy Storage Device with High Capacity and High Power Using Conductive Polymer Composite |
| CN102921473A (en) * | 2012-09-28 | 2013-02-13 | 石河子大学 | Novel nitrogen-modified carbon catalyst carrier and preparation method and use thereof |
| CN103214671A (en) * | 2013-05-07 | 2013-07-24 | 华东交通大学 | Chemical oxidation preparation method for novel N-substituted carboxyl polyaniline |
| CN107394207A (en) * | 2017-06-27 | 2017-11-24 | 宁波墨西科技有限公司 | A kind of graphene composite conductive powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 武文玲: ""不同维度导电聚合物基电极材料的制备及其电化学性能研究"", 《中国博士学位论文全文数据库-工程科技Ⅱ辑》 * |
| 高健: ""基于N-取代羧基聚苯胺共价接枝石墨烯复合材料的合成与电化学性能研究"", 《中国优秀硕士学位论文全文数据库-工程科技Ⅰ辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102468057B (en) | Preparation method for composite electrode material composed of graphite and manganese dioxide | |
| CN106158405B (en) | A kind of nickel hydroxide/graphene nanocomposite material and preparation method thereof, electrode of super capacitor and ultracapacitor | |
| CN101527202A (en) | Oxidized grapheme/polyaniline super capacitor composite electrode material and preparation method and application thereof | |
| CN104658764A (en) | Graphene aerogel three-component compound electrode material of supercapacitor as well as preparation and application | |
| CN103440999B (en) | High-conductivity super-capacitor nanometer MnO 2the preparation method of combination electrode | |
| CN102543464A (en) | ZnO/reduced graphene oxide/polypyrrole ternary composite material preparation method, and application of the ternary composite material | |
| CN106024408B (en) | A kind of ruthenium-oxide-vulcanization carbon/carbon-copper composite material, using and a kind of electrode slice of ultracapacitor | |
| CN106504910B (en) | A kind of anthraquinone molecular cograft carbon/conducting polymer composite material and preparation method thereof | |
| CN111992228A (en) | Molybdenum disulfide and carbon nanotube composite material catalyst, and preparation and application thereof | |
| CN112053861A (en) | In-situ preparation method of three-dimensional conductive MOF @ MXene composite electrode | |
| CN111883366A (en) | A kind of polypyrrole nanosphere@titanium carbide composite material and its preparation method and application | |
| CN111627719B (en) | A conductive polymer hollow sphere PACP@titanium carbide composite material and preparation method thereof | |
| CN110611092A (en) | A kind of preparation method of nano-silica/porous carbon lithium ion battery negative electrode material | |
| CN109167043A (en) | Solvent heat chain polymerization method prepares macromolecule combination electrode material | |
| CN106024425B (en) | A kind of preparation method of CNT/cotton compound | |
| CN107910201A (en) | A kind of preparation method of laminar composite | |
| CN102903528B (en) | Method for rapidly preparing conducting carbon and ruthenium oxide combination electrode material | |
| CN107275124A (en) | A kind of preparation method of film-type electrode of super capacitor | |
| CN105655133A (en) | Cathode material of composite tantalum capacitor and preparation method of cathode material | |
| CN104637701A (en) | Method for preparing graphene-based vanadium pentoxide nanowire super capacitor electrode material | |
| CN102010594A (en) | A kind of preparation method of conductive polymer/silsesquioxane composite electrode material | |
| CN112687477B (en) | Preparation method and application of double transition metal phosphide graphene composite CoNiP-rGO | |
| CN106128802B (en) | A kind of preparation method for the electrode material of supercapacitor | |
| CN107104005A (en) | A kind of preparation method of NiO@graphene fiber super capacitor electrode materials | |
| CN110233057A (en) | Polyaniline nano-line/graphene hollow sphere-graphene oxide preparation and application |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20181218 |
|
| WW01 | Invention patent application withdrawn after publication |