CN107706391B - Carbon-based composite material of low-temperature lithium ion battery and preparation method thereof - Google Patents

Carbon-based composite material of low-temperature lithium ion battery and preparation method thereof Download PDF

Info

Publication number
CN107706391B
CN107706391B CN201710959073.7A CN201710959073A CN107706391B CN 107706391 B CN107706391 B CN 107706391B CN 201710959073 A CN201710959073 A CN 201710959073A CN 107706391 B CN107706391 B CN 107706391B
Authority
CN
China
Prior art keywords
temperature
carbon
lithium ion
composite material
low
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
CN201710959073.7A
Other languages
Chinese (zh)
Other versions
CN107706391A (en
Inventor
丁建宁
徐江
袁宁一
周小双
朱文俊
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.)
Jiangsu University
Yangzhou University
Changzhou University
Original Assignee
Jiangsu University
Changzhou University
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 Jiangsu University, Changzhou University filed Critical Jiangsu University
Priority to CN201710959073.7A priority Critical patent/CN107706391B/en
Publication of CN107706391A publication Critical patent/CN107706391A/en
Application granted granted Critical
Publication of CN107706391B publication Critical patent/CN107706391B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 relates to a carbon-based composite material of a low-temperature lithium ion battery and a preparation method thereof. The composite material has the structural characteristics that: the carbon nano tube with excellent mechanical property and electrical conductivity is supported between the sheets of the expanded graphite, so that the stacking of the graphite sheets is prevented, the electrical conductivity and stability of the structure are enhanced, and the rapid transmission of ions is accelerated. Meanwhile, the mesh-shaped holes are activated on the graphite sheet layer, so that ions can be vertically transmitted, and a transmission path is greatly shortened, thereby realizing the high-rate performance and the low-temperature performance of the graphite sheet layer as a lithium ion negative electrode material.

Description

Carbon-based composite material of low-temperature lithium ion battery and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a carbon-based composite material of a low-temperature lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries have been widely used in various fields as green and environmentally friendly energy sources, but their use in special fields such as aviation, aerospace, and military is limited due to poor low temperature performance. Generally, when the temperature is reduced to-10 ℃, the discharge capacity and the working voltage of the lithium ion storage battery are reduced, and particularly the working performance in a low-temperature environment below-30 ℃ is poor. The graphite negative electrode is extremely difficult to insert lithium at low temperature, and the main reasons for the phenomenon are that the diffusion rate of lithium ions in the graphite negative electrode is low at low temperature, and the charge transfer resistance on an electrode/electrolyte interface is high in the lithium inserting process. Therefore, the low-temperature performance of the lithium ion battery is mainly influenced by the transmission and diffusion of lithium ions in the negative electrode material, and the key for solving the low-temperature performance is to improve the diffusion rate of the lithium ions in the graphite negative electrode material.
The carbon nano tube as a nano material has good conductivity, large length-diameter ratio, large specific surface area and a mesoporous structure which is beneficial to the migration of lithium ions in and out, is an ideal conductive agent of the lithium ion battery, and the hollow structure of the carbon nano tube conductive agent can be used as a warehouse of electrolyte, so that the lithium ions are conveniently transmitted in the electrode, and therefore the lithium ions are easier to be inserted and extracted between a positive electrode and a negative electrode, the electrode polarization is reduced, and the discharge platform and the discharge capacity of the battery at low temperature are improved. Meanwhile, the Expanded Graphite (EG) not only has the excellent performance of natural flake graphite, but also has the excellent characteristics of light weight, good electrical and thermal conductivity, easy molding and the like, so that the EG also receives wide attention in the low-temperature field.
Aiming at the problem that the current graphite cathode material cannot meet the requirement of a lithium ion battery on good electrochemical performance at a low temperature, the invention provides a novel expanded graphite/carbon nanotube composite material and a preparation method thereof.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the carbon-based composite material of the low-temperature lithium ion battery is provided, and the lithium ion battery assembled by the composite material realizes high rate performance and excellent charge and discharge performance at low temperature.
The technical scheme adopted by the invention for solving the technical problems is as follows: providing a carbon-based composite material of a low-temperature lithium ion battery: the expanded graphite/multi-wall carbon nanotube is characterized in that the expanded graphite is composed of graphite sheet layers, each graphite sheet layer is provided with mesh-shaped holes, and the multi-wall carbon nanotube is supported among the graphite sheet layers.
The preparation method of the carbon-based composite material comprises the following steps:
(1) weighing expandable graphite powder, putting the expandable graphite powder into a metal closed container, and putting the metal closed container into a muffle furnace for high-temperature expansion to obtain expanded graphite;
(2) ultrasonically dispersing the expanded graphite in water to obtain a uniform expanded graphite aqueous solution;
(3) ultrasonically dispersing a multi-wall carbon nano tube in water to obtain a carbon nano tube aqueous solution;
(4) ultrasonically mixing the expanded graphite aqueous solution and the carbon nano tube aqueous solution uniformly, and adding ZnCl2Magnetic stirring the aqueous solution until the aqueous solution is uniformly mixed to obtain a mixed solution;
(5) drying the mixed solution at high temperature to obtain a sample;
(6) grinding the sample into powder by using a mortar, and putting the powder into a tube furnace to perform high-temperature activation in an argon environment to obtain an activated sample;
(7) and (3) centrifugally washing and drying the activated sample by using hydrochloric acid and deionized water respectively to obtain the carbon-based composite material of the low-temperature lithium ion battery.
As a preferred embodiment of the invention, the mass of the expandable graphite powder in the step (1) is 1-2 g, the temperature in the muffle furnace is 950-1050 ℃, and the high-temperature expansion time is 28-32 s.
As a preferred embodiment of the present invention, the mass of the expanded graphite in the step (2) is 0.7 to 1g, and the volume of the water is 40 to 60 ml.
As a preferred embodiment of the present invention, PEGMO is added in the step (2) during ultrasonic dispersion, and the amount of PEGMO added is 1-3 ml.
As a preferred embodiment of the present invention, in the step (3), the mass of the multi-walled carbon nanotubes is 20-40mg, the volume of the water is 20-50ml, and the diameter of the multi-walled carbon nanotubes is 20-40 nm.
As a preferred embodiment of the present invention, SDBS is added to water in step (3) before ultrasonic dispersion, and the amount of the added SDBS is 2-4 mg.
As a preferred embodiment of the inventionFor example, in step (4), 18 to 22ml of 0.6mol/L ZnCl are added2And (3) water solution, wherein the ultrasonic mixing time is 28-32min, and the magnetic stirring time is 3-5 h.
As a preferred embodiment of the present invention, the high temperature drying in step (5) is: air-blast drying at 90-110 deg.C for 9-12 h.
As a preferred embodiment of the present invention, the temperature of the high temperature activation in step (6) is 950-.
As a preferred embodiment of the present invention, the hydrochloric acid concentration in the step (7) is 5%.
The invention has the beneficial effects that: the preparation method of the cathode material is simple, high in efficiency and good in stability, is beneficial to realizing industrial mass production, and greatly improves the low-temperature performance of the lithium ion battery. The carbon-based composite material of the low-temperature lithium ion battery prepared by the method is a novel structure anode material of the mesh-shaped expanded graphite/carbon nano tube, and has the following specific advantages: (1) the expanded graphite has good electric and heat conducting properties, and a large number of unique reticular microporous structures are arranged inside the expanded graphite and can absorb a large number of ions; (2) the carbon nano tube can be used as a conductive agent to accelerate the transmission of lithium ions in the electrode, so that the lithium ions are easier to be inserted and extracted between the positive electrode and the negative electrode, the electrode polarization is reduced, and the discharge platform and the discharge capacity of the battery at low temperature are improved; the expanded graphite can enter between the expanded graphite sheets to support the expanded graphite to prevent the sheets from collapsing and stacking, so that the stability of the material structure is enhanced, and more channels are provided for ion transmission; (3) the mesh-shaped holes are activated on the graphite sheet layer of the expanded graphite, so that ions can be vertically transmitted, and the transmission path is greatly shortened, thereby realizing the high-rate performance and the low-temperature performance of the expanded graphite as a lithium ion negative electrode material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
fig. 1 is a schematic diagram of a carbon-based composite material structure of a low-temperature lithium ion battery prepared in the present invention, wherein 1 is a graphite sheet layer, 2 is a carbon nanotube, and 3 is a hole;
fig. 2 is a scanning electron microscope image and a transmission electron microscope image of a carbon-based composite material of a low-temperature lithium ion battery prepared in example three of the present invention;
fig. 3 is an electrochemical test chart of a lithium ion battery assembled by a carbon-based composite material of the low-temperature lithium ion battery prepared in the fourth embodiment of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. In addition, PVDF represents polytetrafluoroethylene, Super p represents conductive carbon black, PEG400MO represents polyethylene glycol oleate 400, and SDBS represents sodium dodecylbenzenesulfonate.
The preparation method of the carbon-based composite material of the low-temperature lithium ion battery comprises the following steps:
weighing expandable graphite powder, putting the expandable graphite powder into a metal closed container, and putting the metal closed container into a muffle furnace for high-temperature expansion to obtain the expanded graphite.
Specifically, 1-2 g of expandable graphite powder is weighed and placed in a metal closed container, and the metal closed container is placed in a muffle furnace to be expanded for 28-32s at the high temperature of 950-1050 ℃, so that the expandable graphite is obtained.
And step two, ultrasonically dispersing the expanded graphite in water to obtain a uniform expanded graphite aqueous solution.
In one embodiment, 0.7-1g of expanded graphite is ultrasonically dispersed in 40-60ml of water, and 1-3ml of PEGMO is added during ultrasonic dispersion to promote the dispersion of the expanded graphite in the water, so as to obtain a uniform expanded graphite aqueous solution.
And step three, ultrasonically dispersing the multi-wall carbon nano tube in water to obtain a carbon nano tube aqueous solution.
In one embodiment, 2-4mg of SDBS (sodium dodecyl benzene sulfonate) surfactant is added into water to promote dispersion of carbon nanotubes, and 20-40mg of multi-walled carbon nanotubes with the diameter of 20-40nm are ultrasonically dispersed in 20-50ml of water to obtain the carbon nanotube aqueous solution.
Step four, after the expanded graphite aqueous solution and the carbon nano tube aqueous solution are mixed uniformly by ultrasound, ZnCl is added2And (3) magnetically stirring the aqueous solution until the aqueous solution is uniformly mixed to obtain a mixed solution.
In one embodiment, the expanded graphite aqueous solution and the carbon nano tube aqueous solution are ultrasonically mixed for 28-32min, and 18-22ml of 0.6mol/L ZnCl is added after the mixture is uniform2And magnetically stirring the aqueous solution for 3-5 hours until the aqueous solution is uniformly mixed to obtain a mixed solution.
And step five, drying the mixed solution at high temperature to obtain a sample.
Specifically, the mixed solution is dried by blowing at 90-110 ℃ for 9-12h to prepare a sample.
And step six, grinding the sample into powder by using a mortar, and putting the powder into a tube furnace for high-temperature activation in an argon environment to obtain an activated sample.
Specifically, the sample is ground into powder by a mortar and then is put into a tube furnace to be activated for 1-3h at the temperature of 950-.
And seventhly, centrifugally washing and drying the activated sample by using hydrochloric acid and deionized water respectively to obtain the carbon-based composite material of the low-temperature lithium ion battery.
Specifically, the activated sample is centrifugally washed and dried by using 5% hydrochloric acid and a large amount of deionized water respectively to obtain the carbon-based composite material of the low-temperature lithium ion battery.
The vermicular expanded graphite is prepared by a high-temperature thermal expansion method, an expanded graphite aqueous solution, a carbon nano tube aqueous solution and a zinc chloride aqueous solution are uniformly mixed, and the composite material is obtained by high-temperature activation of inert gas. Referring to fig. 1, fig. 1 is a schematic view of a carbon-based composite material structure of a low-temperature lithium ion battery prepared in the present invention, wherein 1 is a graphite sheet layer, 2 is a carbon nanotube, and 3 is a hole. As shown in fig. 1, the composite material is composed of expanded graphite and multi-walled carbon nanotubes 2, wherein the expanded graphite is composed of a plurality of graphite sheet layers 1, each graphite sheet layer 1 is provided with mesh-shaped holes, the multi-walled carbon nanotubes 2 are supported among the plurality of graphite sheet layers 1, and the composite material has the structural characteristics that: the carbon nano tube with excellent mechanical property and electrical conductivity is supported between the sheets of the expanded graphite, so that the stacking of the graphite sheets is prevented, the electrical conductivity and stability of the structure are enhanced, and the rapid transmission of ions is accelerated. Meanwhile, the mesh-shaped holes are activated on the graphite sheet layer, so that ions can be vertically transmitted, and a transmission path is greatly shortened, thereby realizing the high-rate performance and the low-temperature performance of the graphite sheet layer as a lithium ion negative electrode material.
Four embodiments which can fully embody the content of the invention are introduced below by combining with a preparation method of a carbon-based composite material of a low-temperature lithium ion battery:
the first embodiment is as follows:
carbon-based composite material for manufacturing low-temperature lithium ion battery
Step 1: weighing 1g of expandable graphite powder, putting the expandable graphite powder into a metal closed container, and placing the container in a muffle furnace at 950 ℃ for high-temperature expansion for about 28 seconds to obtain the expanded graphite.
Step 2: 1ml of PEG400MO was dispersed in 40ml of water, 0.7g of expanded graphite was added thereto, and the mixture was ultrasonically dispersed for 30 minutes to obtain a uniform expanded graphite aqueous solution.
And step 3: carbon nanotube powder treatment: putting 0.5g of carbon nanotube powder into a reaction kettle with a volume ratio of concentrated nitric acid to water of 1: 2, stirring and soaking for more than 24 hours, pouring the turbid liquid into a centrifuge tube, centrifuging to be neutral, taking out and drying in a vacuum oven at 80 ℃ for 12 hours. And adding the dried 20mg of multi-walled carbon nanotube and 2mg of SDBS into 20ml of water, and performing ultrasonic dispersion for 3 hours to obtain a carbon nanotube aqueous solution.
And 4, step 4: mixing the expanded graphite water solution and the carbon nano tube water solution for 28min by ultrasonic treatment to obtain uniform mixed solution, and then adding 18ml of 0.6mol/L ZnCl2Magnetically stirring the aqueous solution for 3 hours until the aqueous solution is uniformly mixed;
and 5: putting the obtained mixed solution into a forced air oven to be dried for 9 hours at the temperature of 90 ℃ to obtain a sample;
step 6: grinding a sample into powder by using a mortar, filling the powder by using a crucible, putting the powder into a tubular furnace, heating to 950 ℃ at the speed of 5 ℃/min under the argon environment, and preserving heat for 1h to obtain an activated sample;
and 7: and soaking the activated samples with 5% hydrochloric acid respectively, performing centrifugal washing with a large amount of deionized water, and drying to obtain the carbon-based composite material of the low-temperature lithium ion battery.
Example two:
carbon-based composite material for manufacturing low-temperature lithium ion battery
Step 1: weighing 2g of expandable graphite powder, putting the expandable graphite powder into a metal closed container, and placing the container in a muffle furnace at 1050 ℃ for high-temperature expansion for about 32s to obtain the expanded graphite.
Step 2: 3ml of PEG400MO is dispersed in 60ml of water, 1g of expanded graphite is weighed and added, and ultrasonic dispersion is carried out for 30 minutes to obtain uniform expanded graphite aqueous solution.
And step 3: carbon nanotube powder treatment: putting 0.5g of carbon nanotube powder into a reaction kettle with a volume ratio of concentrated nitric acid to water of 1: 2, stirring and soaking for more than 24 hours, pouring the turbid liquid into a centrifuge tube, centrifuging to be neutral, taking out and drying in a vacuum oven at 80 ℃ for 12 hours. And adding the dried 40mg of multi-wall carbon nano tube and 4mg of SDBS into 50ml of water, and performing ultrasonic dispersion for 3 hours to obtain a carbon nano tube aqueous solution.
And 4, step 4: mixing the expanded graphite water solution and the carbon nano tube water solution for 32min by ultrasonic treatment to obtain uniform mixed solution, and then adding 22ml of 0.6mol/L ZnCl2Magnetic stirring the aqueous solution for 5 hours until the aqueous solution is uniformly mixed;
and 5: putting the obtained mixed solution into a forced air oven to be dried for 12 hours at the temperature of 110 ℃ to obtain a sample;
step 6: grinding a sample into powder by using a mortar, filling the powder by using a crucible, putting the powder into a tubular furnace, heating the powder to 1050 ℃ at the speed of 5 ℃/min under the argon environment, and preserving the temperature for 3 hours to obtain an activated sample;
and 7: and soaking the activated samples with 5% hydrochloric acid respectively, performing centrifugal washing with a large amount of deionized water, and drying to obtain the carbon-based composite material of the low-temperature lithium ion battery.
Example three:
carbon-based composite material for manufacturing low-temperature lithium ion battery
Step 1: weighing 1.2g of expandable graphite powder, putting the expandable graphite powder into a metal closed container, and placing the container in a muffle furnace at 1000 ℃ for high-temperature expansion for about 30s to obtain the expandable graphite.
Step 2: 2ml of PEG400MO is dispersed in 50ml of water, 1g of expanded graphite is weighed and added, and ultrasonic dispersion is carried out for 30 minutes to obtain uniform expanded graphite aqueous solution.
And step 3: carbon nanotube powder treatment: putting 0.5g of carbon nanotube powder into a reaction kettle with a volume ratio of concentrated nitric acid to water of 1: 2, stirring and soaking for more than 24 hours, pouring the turbid liquid into a centrifuge tube, centrifuging to be neutral, taking out and drying in a vacuum oven at 80 ℃ for 12 hours. And adding the dried 40mg of multi-walled carbon nanotube and 3mg of SDBS into 20ml of water, and performing ultrasonic dispersion for 3 hours to obtain a carbon nanotube aqueous solution.
And 4, step 4: mixing the expanded graphite water solution and the carbon nano tube water solution for 30min by ultrasonic treatment to obtain uniform mixed solution, and then adding 20ml of 0.6mol/L ZnCl2Magnetic stirring the aqueous solution for 4 hours until the aqueous solution is uniformly mixed;
and 5: putting the obtained mixed solution into a forced air oven for drying at 100 ℃ to obtain a sample;
step 6: grinding a sample by using a mortar into powder, filling the powder by using a crucible, putting the powder into a tubular furnace, heating the powder to 1000 ℃ at a speed of 5 ℃/min under an argon environment, and preserving the temperature for 2 hours to obtain an activated sample;
and 7: and soaking the activated samples with 5% hydrochloric acid respectively, performing centrifugal washing with a large amount of deionized water, and drying to obtain the carbon-based composite material of the low-temperature lithium ion battery.
Referring to fig. 2, fig. 2 is a scanning electron microscope image and a transmission electron microscope image of the carbon-based composite material of the low-temperature lithium ion battery prepared in the third embodiment of the present invention, and it can be seen from fig. 2 that all graphite sheets are expanded, many mesh-shaped hole defects exist on the sheets, and the carbon nanotubes are supported between the graphite sheets in a crossed manner.
Example four:
battery for manufacturing carbon-based composite material with low-temperature lithium ion battery
The difference between the present embodiment and the third embodiment is: after completion of step 7, the obtained material was mixed with PVDF and the conductive agent Super p at a ratio of 90: 5: 5, grinding uniformly, adding a small amount of water to prepare slurry, coating the slurry on an aluminum foil by a coating machine, putting the aluminum foil into a vacuum oven, drying for 12 hours in vacuum at 100 ℃, preparing an electrode slice, and cutting the electrode slice into small round slices with the diameter of 15mm by a cutting machine, wherein the mass of each slice is about 1 mg cm-2And then assembled into 2025 button cells in a glove box, where the separator was a commercial separator (Celgard 2400), a commercial 1M LiPF6 blend EC, DEC (1: 1 = v: v, analytical grade) as the electrolyte, and lithium foil as the counter electrode sheet. And finally, carrying out charge and discharge tests on the mounted button cell by using a blue light tester, and carrying out charge and discharge tests under the conditions of 0 degree, -20 degrees and-40 degrees respectively.
Referring to fig. 3, fig. 3 is an electrochemical test chart of a lithium ion battery assembled by a carbon-based composite material of a low-temperature lithium ion battery prepared in example four of the present invention. It can be seen from fig. 3 that the negative electrode material has excellent charge and discharge properties when subjected to charge and discharge tests under low temperature conditions.
It should be understood by those skilled in the art that one of the features or objects of the present invention is to: the carbon-based composite material of the low-temperature lithium ion battery prepared by the method comprises the following steps: (1) the carbon nano tube with excellent mechanical property is supported between the sheets of the expanded graphite, so that the stacking of the graphite sheets is prevented, the conductivity and the stability of the structure are enhanced, and the rapid transmission of ions is accelerated; (2) the graphite sheet layer is activated to form mesh-shaped holes, so that ions can be vertically transmitted, and a transmission path is greatly shortened, thereby realizing the high-rate performance and the low-temperature performance of the graphite sheet layer as a lithium ion negative electrode material. The assembled lithium ion battery can be normally used at the temperature of minus 40 ℃.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. A carbon-based composite material for a low temperature lithium ion battery, comprising: the expanded graphite comprises a plurality of graphite sheet layers, wherein each graphite sheet layer is provided with a mesh-shaped hole, the multiwalled carbon nanotube is supported among the graphite sheet layers, and the preparation method comprises the following steps:
(1) weighing expandable graphite powder, putting the expandable graphite powder into a metal closed container, and putting the metal closed container into a muffle furnace for high-temperature expansion to obtain expanded graphite;
(2) ultrasonically dispersing the expanded graphite in water to obtain a uniform expanded graphite aqueous solution;
(3) ultrasonically dispersing a multi-wall carbon nano tube in water to obtain a carbon nano tube aqueous solution;
(4) ultrasonically mixing the expanded graphite aqueous solution and the carbon nano tube aqueous solution uniformly, and adding ZnCl2Magnetic stirring the aqueous solution until the aqueous solution is uniformly mixed to obtain a mixed solution;
(5) drying the mixed solution at high temperature to obtain a sample;
(6) grinding the sample into powder by using a mortar, and putting the powder into a tube furnace to perform high-temperature activation in an argon environment to obtain an activated sample;
(7) and (3) centrifugally washing and drying the activated sample by using hydrochloric acid and deionized water respectively to obtain the carbon-based composite material of the low-temperature lithium ion battery.
2. A preparation method of a carbon-based composite material of a low-temperature lithium ion battery is characterized by comprising the following steps:
(1) weighing expandable graphite powder, putting the expandable graphite powder into a metal closed container, and putting the metal closed container into a muffle furnace for high-temperature expansion to obtain expanded graphite;
(2) ultrasonically dispersing the expanded graphite in water to obtain a uniform expanded graphite aqueous solution;
(3) ultrasonically dispersing a multi-wall carbon nano tube in water to obtain a carbon nano tube aqueous solution;
(4) ultrasonically mixing the expanded graphite aqueous solution and the carbon nano tube aqueous solution uniformly, and adding ZnCl2Magnetic stirring the aqueous solution until the aqueous solution is uniformly mixed to obtain a mixed solution;
(5) drying the mixed solution at high temperature to obtain a sample;
(6) grinding the sample into powder by using a mortar, and putting the powder into a tube furnace to perform high-temperature activation in an argon environment to obtain an activated sample;
(7) and (3) centrifugally washing and drying the activated sample by using hydrochloric acid and deionized water respectively to obtain the carbon-based composite material of the low-temperature lithium ion battery.
3. The preparation method of the carbon-based composite material of the low-temperature lithium ion battery according to claim 2, characterized in that: the mass of the expandable graphite powder in the step (1) is 1-2 g, the temperature in the muffle furnace is 950-1050 ℃, and the high-temperature expansion time is 28-32 s.
4. The preparation method of the carbon-based composite material of the low-temperature lithium ion battery according to claim 2, characterized in that: in the step (2), the mass of the expanded graphite is 0.7-1g, the volume of the water is 40-60ml, and in the step (2), PEGMO is added during ultrasonic dispersion, and the addition amount of the PEGMO is 1-3 ml.
5. The preparation method of the carbon-based composite material of the low-temperature lithium ion battery according to claim 2, characterized in that: in the step (3), the mass of the multi-wall carbon nano-tube is 20-40mg, the volume of the water is 20-50ml, and the diameter of the multi-wall carbon nano-tube is 20-40 nm.
6. The preparation method of the carbon-based composite material of the low-temperature lithium ion battery according to claim 2, characterized in that: and (3) adding SDBS into water before ultrasonic dispersion, wherein the addition amount of the SDBS is 2-4 mg.
7. The preparation method of the carbon-based composite material of the low-temperature lithium ion battery according to claim 2, characterized in that: in the step (4), 18-22ml of 0.6mol/L ZnCl is added2And (3) water solution, wherein the ultrasonic mixing time is 28-32min, and the magnetic stirring time is 3-5 h.
8. The preparation method of the carbon-based composite material of the low-temperature lithium ion battery according to claim 2, characterized in that: the high-temperature drying in the step (5) comprises the following steps: air-blast drying at 90-110 deg.C for 9-12 h.
9. The preparation method of the carbon-based composite material of the low-temperature lithium ion battery according to claim 2, characterized in that: the temperature of the high-temperature activation in the step (6) is 950-1050 ℃, and the time is 1-3 h.
10. The preparation method of the carbon-based composite material of the low-temperature lithium ion battery according to claim 2, characterized in that: the hydrochloric acid concentration in the step (7) is 5%.
CN201710959073.7A 2017-10-16 2017-10-16 Carbon-based composite material of low-temperature lithium ion battery and preparation method thereof Active CN107706391B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710959073.7A CN107706391B (en) 2017-10-16 2017-10-16 Carbon-based composite material of low-temperature lithium ion battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710959073.7A CN107706391B (en) 2017-10-16 2017-10-16 Carbon-based composite material of low-temperature lithium ion battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107706391A CN107706391A (en) 2018-02-16
CN107706391B true CN107706391B (en) 2020-06-02

Family

ID=61184393

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710959073.7A Active CN107706391B (en) 2017-10-16 2017-10-16 Carbon-based composite material of low-temperature lithium ion battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107706391B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109585832B (en) * 2018-12-05 2021-02-09 中南大学 Sulfur-doped microcrystalline graphite, preparation method thereof and application of sulfur-doped microcrystalline graphite as negative electrode material of sodium-ion battery
CN109713302A (en) * 2018-12-10 2019-05-03 江苏大学 Under a kind of ultralow temperature can big multiplying power charge and discharge lithium ion battery and preparation method thereof
CN114551800A (en) * 2022-01-29 2022-05-27 宁德新能源科技有限公司 Carbon-based conductive agent, secondary battery and power utilization device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102610827A (en) * 2012-03-28 2012-07-25 长沙星城微晶石墨有限公司 Conductive additive for preparing power lithium ion battery cathode material and preparation method thereof
CN105948029A (en) * 2016-05-09 2016-09-21 东华大学 Graphene roll/carbon nanotube composite aerogel material, preparation and application thereof
CN106025297A (en) * 2016-07-29 2016-10-12 盐城工学院 Electrode preparation method of new energy source automobile fuel cell
CN107146887A (en) * 2017-04-11 2017-09-08 上海交通大学 Carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102610827A (en) * 2012-03-28 2012-07-25 长沙星城微晶石墨有限公司 Conductive additive for preparing power lithium ion battery cathode material and preparation method thereof
CN105948029A (en) * 2016-05-09 2016-09-21 东华大学 Graphene roll/carbon nanotube composite aerogel material, preparation and application thereof
CN106025297A (en) * 2016-07-29 2016-10-12 盐城工学院 Electrode preparation method of new energy source automobile fuel cell
CN107146887A (en) * 2017-04-11 2017-09-08 上海交通大学 Carbon nanometer three-dimensional structure composite for negative electrode of lithium ion battery and preparation method thereof

Also Published As

Publication number Publication date
CN107706391A (en) 2018-02-16

Similar Documents

Publication Publication Date Title
CN102208608B (en) Preparation method of carbon-sulfur composite material for lithium ion battery carbon cathode material
CN106450192A (en) Silicon/carbon composite material for lithium ion battery and preparation method and application thereof
CN107221654B (en) Three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and preparation method thereof
CN104319371B (en) A kind of preparation method of lithium ion battery SnS2/CNTs/PPy composite negative pole material
CN106410164B (en) A kind of anode material and its preparation method and application
CN107706391B (en) Carbon-based composite material of low-temperature lithium ion battery and preparation method thereof
CN109346702B (en) Negative electrode material of lithium battery and preparation method thereof
CN107634210B (en) High-performance lithium/sodium battery negative electrode material and preparation method thereof
CN106920936B (en) High-performance organic lithium ion battery positive electrode material and preparation method thereof
CN106532012A (en) Sulfur-biomass carbon/transition metal composite electrode material and preparation method and application thereof
CN112018346A (en) Phosphorus-doped CoSe2Mxene composite material and preparation method thereof
CN110212162B (en) Flexible gel sulfur positive electrode for lithium-sulfur battery and preparation method
CN108777303A (en) A kind of biomass derived hard carbon/graphene anode material of lithium-ion battery and preparation method thereof
CN106654192A (en) Tin sulfide/graphene sodium ion battery composite cathode material and preparation method thereof
CN106848250B (en) Carbon-sulfur material with high sulfur content and preparation method thereof
CN107681130A (en) A kind of preparation method of the lithium sulfur battery anode material of solid electrolyte
CN108539143A (en) A method of quickly preparing high-capacity lithium ion cell silicon based anode material
CN104779379A (en) Novel sulfur and carbon composite material for lithium secondary battery, and preparation method thereof
CN109755542B (en) Sodium-sulfur battery positive electrode material and preparation method thereof
CN104600265B (en) A kind of carbon sulphur composite positive pole and preparation method thereof
CN113506860A (en) Carbon nanotube-in-tube @ selenium composite material and preparation method and application thereof
CN110518227B (en) Lithium-sulfur battery positive electrode material and preparation method thereof
CN108615867A (en) A kind of organic macromolecule negative material and preparation method thereof for secondary cell
CN105826552A (en) Method for producing graphene-composited lithium cobalt oxide positive electrode material
CN110336033B (en) Battery positive electrode material, preparation method thereof and lithium-sulfur battery

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
TA01 Transfer of patent application right

Effective date of registration: 20181015

Address after: 213000 No. 1, Hu Hu Road, Wujin District, Changzhou, Jiangsu

Applicant after: Changzhou University

Applicant after: Jiangsu University

Address before: 213100 Changzhou University, 1 Hu Hu Road, Wujin District, Changzhou, Jiangsu

Applicant before: Changzhou University

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20230515

Address after: 225009 No. 88, South University Road, Jiangsu, Yangzhou

Patentee after: YANGZHOU University

Patentee after: CHANGZHOU University

Patentee after: JIANGSU University

Address before: 213000 No. 1, Hu Hu Road, Wujin District, Changzhou, Jiangsu

Patentee before: CHANGZHOU University

Patentee before: JIANGSU University

TR01 Transfer of patent right