CN107706391A - A kind of C-base composte material of low-temperature lithium ion battery and preparation method thereof - Google Patents
A kind of C-base composte material of low-temperature lithium ion battery and preparation method thereof Download PDFInfo
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- CN107706391A CN107706391A CN201710959073.7A CN201710959073A CN107706391A CN 107706391 A CN107706391 A CN 107706391A CN 201710959073 A CN201710959073 A CN 201710959073A CN 107706391 A CN107706391 A CN 107706391A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 present invention relates to a kind of C-base composte material of low-temperature lithium ion battery and preparation method thereof, vermiform expanded graphite is prepared by high-temperature heat expansion method, the expanded graphite aqueous solution, carbon nano-tube aqueous solutions and solder(ing)acid are uniformly mixed, composite is obtained by inert gas high-temperature activation.The composite is structurally characterized in that：Between CNT with excellent mechanical properties and electric conductivity is supported on the lamella of expanded graphite, the stacking of graphite flake layer is prevented, enhances the electric conductivity and stability of structure, accelerates the quick transmission of ion.Meanwhile the hole of mesh is activated out on graphite flake layer, enable ion vertical transfer, substantially reduce transmission path, it is achieved thereby that its high rate capability and cryogenic property as ion cathode material lithium.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, and in particular to a kind of low-temperature lithium ion battery it is carbon-based
Composite and preparation method thereof.
Background technology
Lithium ion battery has been widely used for various fields as the green energy, but poor cryogenic property makes
It is restricted in the application of the special dimension such as Aeronautics and Astronautics and military affairs.Typically when temperature is down to -10 DEG C, lithium ion electric power storage
The discharge capacity and operating voltage in pond can all reduce, and the service behaviour particularly below -30 DEG C in low temperature environment is poor.Graphite
Process of intercalation is extremely difficult at low temperature for negative pole, and the main reason for causing this phenomenon is lithium ion in graphite cathode at low temperature
Diffusion rate is small, the charge transfer impedance in process of intercalation on electrode/electrolyte interface is larger.Therefore the low temperature of lithium ion battery
Performance mainly by transmission of the lithium ion in negative material and extends influence, and improves the lithium ion diffusion in graphite cathode material
Speed is the key for solving cryogenic property.
CNT has good electric conductivity and big draw ratio, specific surface area and is advantageous to as a kind of nano material
The meso-hole structure of lithium ion entry/leave, is the conductive agent of preferable lithium ion battery, the hollow structure of carbon nanotube conducting agent
The transmission of lithium ion in the electrodes can be facilitated as the warehouse of electrolyte, so that lithium ion is easier in positive and negative interpolar
Embedded and deintercalation, reduces electrode polarization, improves battery discharge platform at low temperature and discharge capacity.Meanwhile expand stone
Ink（EG）Not only there is the premium properties of natural flake graphite, also with light weight, electrical and thermal conductivity is good, the excellent spy such as easy-formation
Property, it is also received significant attention in low temperature field.
It can not meet that lithium ion battery has good chemical property at low temperature for current graphite cathode material
Requirement, the invention provides a kind of expansible graphite/carbon nanometer tube composite materials and preparation method thereof.
The content of the invention
The technical problem to be solved in the present invention is：Present in overcoming graphite as negative material and applying at low ambient temperatures
The problem of limitation, there is provided a kind of preparation method of the C-base composte material of low-temperature lithium ion battery, utilize the composite group
The lithium ion battery of dress realizes high rate capability and excellent charge-discharge performance at low temperature.
The technical solution adopted for the present invention to solve the technical problems is：A kind of the carbon-based multiple of low-temperature lithium ion battery is provided
Condensation material：Expanded graphite/multi-walled carbon nanotube, expanded graphite are made up of graphite flake layer, have mesh on every graphite flake layer
Hole, the multi-walled carbon nanotube is supported between the multi-disc graphite flake layer.
The preparation method of above-mentioned C-base composte material comprises the following steps：
(1) weigh expandable powdered graphite to be put into metal enclosed container, it is expanded to be placed in Muffle furnace high temperature, obtains expanding stone
Ink；
(2) by the expanded graphite ultrasonic disperse in water, the uniform expanded graphite aqueous solution is obtained；
(3) multi-walled carbon nanotube ultrasonic disperse is obtained into carbon nano-tube aqueous solutions in water；
(4) by the expanded graphite aqueous solution and the carbon nano-tube aqueous solutions ultrasonic mixing it is uniform after, add ZnCl2It is water-soluble
Liquid, magnetic agitation obtain mixed solution to uniform mixing；
(5) mixed solution is subjected to high temperature drying, sample is made；
(6) sample is put into tube furnace under ar gas environment with mortar grinder into powder and carries out high-temperature activation, lived
Change sample；
(7) activated sample is subjected to centrifuge washing, drying with hydrochloric acid, deionized water respectively, obtains low-temperature lithium ion battery
C-base composte material.
As the present invention a preferred embodiment, the quality of expandable powdered graphite described in step (1) be 1 ~
2g, the temperature in the Muffle furnace is 950-1050 DEG C, and the high temperature puffing time is 28-32s.
As the preferred embodiment of the present invention, the quality of expanded graphite described in step (2) is 0.7-1g, described
The volume of water is 40-60ml.
As the preferred embodiment of the present invention, in step (2), PEGMO is added in ultrasonic disperse, it is described
PEGMO addition is 1-3ml.
As the preferred embodiment of the present invention, the quality of multi-walled carbon nanotube described in step (3) is 20-
40mg, the volume of the water is 20-50ml, a diameter of 20-40nm of the multi-walled carbon nanotube.
As the preferred embodiment of the present invention, in step (3) before ultrasonic disperse, SDBS is added in water, institute
The addition for stating SDBS is 2-4mg.
As the preferred embodiment of the present invention, the mol/L of 18-22ml 0.6 ZnCl is added in step (4)2Water
Solution, the ultrasonic mixing time are 28-32min, and the magnetic agitation time is 3-5h.
As the preferred embodiment of the present invention, high temperature drying is described in step (5)：Under the conditions of 90-110 DEG C
Forced air drying 9-12h.
As the preferred embodiment of the present invention, the temperature of high-temperature activation described in step (6) is 950-1050 DEG C,
Time is 1-3h.
As the preferred embodiment of the present invention, concentration of hydrochloric acid described in step (7) is 5%.
The beneficial effects of the invention are as follows：The preparation method of the negative material is simple, efficiency high, and stability is good, is advantageous to reality
Existing industrialized production, substantially increase the cryogenic property of lithium ion battery.Low-temperature lithium ion battery prepared by this method
C-base composte material is a kind of new structure negative material of expanded graphite/CNT of mesh, and specific advantage is：
（1）Expanded graphite has good conduction and heat conductivility, and inside has a large amount of unique reticulated macroporous structures adsorbable a large amount of
Ion；（2）CNT can both accelerate the transmission of lithium ion in the electrodes as conductive agent, so that lithium ion is just
Embedded and deintercalation is easier between negative pole, reduces electrode polarization, improves battery discharge platform at low temperature and discharge capacity；
Support expanded graphite prevent caving in and stacking for lamella between expanded graphite lamella can be entered again, so as to enhance material structure
Stability simultaneously for ion transmit more passages are provided；（3）The activated mesh on the graphite flake layer of expanded graphite
Hole, enable ion vertical transfer, substantially reduce transmission path, it is achieved thereby that its height as ion cathode material lithium
High rate performance and cryogenic property.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill of field, without having to pay creative labor, it can also be obtained according to these accompanying drawings other
Accompanying drawing.Wherein：
Fig. 1 is the schematic diagram of the C-base composte material structure of low-temperature lithium ion battery prepared in the present invention, wherein, 1 is stone
Ink sheet layer, 2 be CNT, 3 be hole；
Fig. 2 is the scanning electron microscope (SEM) photograph of the C-base composte material of the low-temperature lithium ion battery prepared by embodiment three and thoroughly in the present invention
Penetrate electron microscope；
Fig. 3 is the lithium ion battery of the C-base composte material assembling of the low-temperature lithium ion battery prepared by example IV in the present invention
Electro-chemical test figure.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, it is below in conjunction with the accompanying drawings and specific real
Applying mode, the present invention is further detailed explanation.
" one embodiment " or " embodiment " referred to herein refers to may be included at least one implementation of the present invention
Special characteristic, structure or characteristic." in one embodiment " that different places occur in this manual not refers both to same
Individual embodiment, nor the single or selective embodiment mutually exclusive with other embodiment.In addition, it is necessary to explanation
It is that PVDF represents polytetrafluoroethylene (PTFE), Super p represent conductive black, and PEG400MO represents polyethylene glycol (PEG) oleate 400, SDBS
Represent neopelex.
A kind of preparation method of the C-base composte material of low-temperature lithium ion battery of the present invention comprises the following steps：
Step 1, weigh expandable powdered graphite and be put into metal enclosed container, it is expanded to be placed in Muffle furnace high temperature, obtains swollen
Swollen graphite.
It is put into metal enclosed container, is placed in Muffle furnace for the expandable powdered graphites of 1 ~ 2g specifically, weighing quality
Expanded 28-32s, obtains expanded graphite at a high temperature of 950-1050 DEG C.
Step 2, by the expanded graphite ultrasonic disperse in water, obtain the uniform expanded graphite aqueous solution.
In one embodiment, by quality be 0.7-1g expanded graphite ultrasonic disperse in 40-60ml water, ultrasound point
It is scattered come promote expanded graphite in water that 1-3ml PEGMO need to be added when scattered, obtains the uniform expanded graphite aqueous solution.
Step 3, by multi-walled carbon nanotube ultrasonic disperse in water, obtain carbon nano-tube aqueous solutions.
In one embodiment, SDBS (neopelex) surfactants that 2-4mg is added in water promote
Enter the scattered of CNT, by 20-40mg a diameter of 20-40nm multi-walled carbon nanotube ultrasonic disperse 20-50ml water
In, obtain carbon nano-tube aqueous solutions.
Step 4, by the expanded graphite aqueous solution and the carbon nano-tube aqueous solutions ultrasonic mixing it is uniform after, add
ZnCl2The aqueous solution, magnetic agitation obtain mixed solution to uniform mixing.
In one embodiment, by the expanded graphite aqueous solution and the carbon nano-tube aqueous solutions ultrasonic mixing 28-
32min, after uniformly, add 18-22ml 0.6 mol/L ZnCl2The aqueous solution, magnetic agitation 3-5h obtain to uniform mixing
To mixed solution.
Step 5, the mixed solution is subjected to high temperature drying, sample is made.
Specifically, by the mixed solution under the conditions of 90-110 DEG C forced air drying 9-12h, be made sample.
Step 6, the sample is put into tube furnace under ar gas environment with mortar grinder into powder and carries out high temperature work
Change, obtain activated sample.
Specifically, the sample is put into tube furnace under ar gas environment with mortar grinder into powder, 950-1050 DEG C
Temperature conditionss under high-temperature activation 1-3h, obtain activated sample.
Step 7, the activated sample is subjected to centrifuge washing, drying with hydrochloric acid, deionized water respectively, obtains low temperature lithium
The C-base composte material of ion battery.
Specifically, by the activated sample respectively with concentration be 5% hydrochloric acid, substantial amounts of deionized water carry out centrifuge washing,
Dry, obtain the C-base composte material of low-temperature lithium ion battery.
Above-mentioned steps, vermiform expanded graphite is prepared by high-temperature heat expansion method, by the expanded graphite aqueous solution, carbon nanometer
The pipe aqueous solution and solder(ing)acid are uniformly mixed, and composite is obtained by inert gas high-temperature activation.Referring to Fig. 1,
Fig. 1 is the schematic diagram of the C-base composte material structure of low-temperature lithium ion battery prepared in the present invention, wherein, 1 is graphite flake
Layer, 2 be CNT, 3 be hole.As shown in figure 1, the composite is made up of expanded graphite and multi-walled carbon nanotube 2, expansion
Graphite is made up of multi-disc graphite flake layer 1, there is the hole of mesh on every graphite flake layer 1, and multi-walled carbon nanotube 2 is supported in more
Between piece graphite flake layer 1, the composite is structurally characterized in that：CNT branch with excellent mechanical properties and electric conductivity
Support between the lamella of expanded graphite, prevent the stacking of graphite flake layer, enhance the electric conductivity and stability of structure, accelerate from
The quick transmission of son.Meanwhile the hole of mesh is activated out on graphite flake layer, enable ion vertical transfer, greatly shorten
Transmission path, it is achieved thereby that its high rate capability and cryogenic property as ion cathode material lithium.
This can be fully demonstrated by introducing four with reference to the preparation method of the C-base composte material of low-temperature lithium ion battery
The embodiment of the content of the invention：
Embodiment one：
Make the C-base composte material of low-temperature lithium ion battery
Step 1：Weigh the expandable powdered graphites of 1g to be put into metal enclosed container, it is swollen to be placed in 950 DEG C of Muffle furnace high temperature
Change about 28s, obtain expanded graphite.
Step 2：1ml PEG400MO is dispersed in 40ml water, then weighs 0.7g expanded graphites and adds, ultrasonic disperse
30 minutes, obtain the uniform expanded graphite aqueous solution.
Step 3：Carbon nanotube powder processing：It is 1 that 0.5g carbon nanotube powders are put into concentrated nitric acid with water volume ratio：2
In 60ml acid solutions, stirring, soak more than 24h, then turbid solution is poured into centrifuge tube and centrifuged to neutrality, at 80 DEG C after taking-up
12h is dried in vacuum drying oven.The 20mg multi-walled carbon nanotubes of drying and 2mg SDBS are added in 20ml water, ultrasonic disperse 3h, obtained
To carbon nano-tube aqueous solutions.
Step 4：The expanded graphite aqueous solution and carbon nano-tube aqueous solutions are mixed into ultrasonic 28min, uniformly mixed molten
Liquid, add 18ml 0.6 mol/L ZnCl2The aqueous solution, magnetic agitation 3h to uniform mixing；
Step 5：Obtained mixed solution is put into 90 DEG C of drying 9h of convection oven, obtains sample；
Step 6：Be put into after sample is installed with mortar grinder into powder with crucible in tube furnace under ar gas environment, with 5 DEG C/
Min is warming up to 950 DEG C, and activated sample is made in insulation 1h；
Step 7：By activated sample respectively with 5% salt acid soak, carry out centrifuge washing with a large amount of deionized waters, dry, obtain low
The C-base composte material of warm lithium ion battery.
Embodiment two：
Make the C-base composte material of low-temperature lithium ion battery
Step 1：Weigh the expandable powdered graphites of 2g to be put into metal enclosed container, it is swollen to be placed in 1050 DEG C of Muffle furnace high temperature
Change about 32s, obtain expanded graphite.
Step 2：3ml PEG400MO is dispersed in 60ml water, then weighs 1g expanded graphites and adds, ultrasonic disperse 30
Minute, obtain the uniform expanded graphite aqueous solution.
Step 3：Carbon nanotube powder processing：It is 1 that 0.5g carbon nanotube powders are put into concentrated nitric acid with water volume ratio：2
In 60ml acid solutions, stirring, soak more than 24h, then turbid solution is poured into centrifuge tube and centrifuged to neutrality, at 80 DEG C after taking-up
12h is dried in vacuum drying oven.The 40mg multi-walled carbon nanotubes of drying and 4mg SDBS are added in 50ml water, ultrasonic disperse 3 hours,
Obtain carbon nano-tube aqueous solutions.
Step 4：The expanded graphite aqueous solution and carbon nano-tube aqueous solutions are mixed into ultrasonic 32min, uniformly mixed molten
Liquid, add 22ml 0.6 mol/L ZnCl2The aqueous solution, magnetic agitation 5h to uniform mixing；
Step 5：Obtained mixed solution is put into 110 DEG C of drying 12h of convection oven, obtains sample；
Step 6：Be put into after sample is installed with mortar grinder into powder with crucible in tube furnace under ar gas environment, with 5 DEG C/
Min is warming up to 1050 DEG C, and activated sample is made in insulation 3h；
Step 7：By activated sample respectively with 5% salt acid soak, carry out centrifuge washing with a large amount of deionized waters, dry, obtain low
The C-base composte material of warm lithium ion battery.
Embodiment three：
Make the C-base composte material of low-temperature lithium ion battery
Step 1：Weigh the expandable powdered graphites of 1.2g to be put into metal enclosed container, be placed in 1000 DEG C of Muffle furnace high temperature
Expanded about 30s, obtains expanded graphite.
Step 2：2ml PEG400MO is dispersed in 50ml water, then weighs 1g expanded graphites and adds, ultrasonic disperse 30
Minute, obtain the uniform expanded graphite aqueous solution.
Step 3：Carbon nanotube powder processing：It is 1 that 0.5g carbon nanotube powders are put into concentrated nitric acid with water volume ratio：2
In 60ml acid solutions, stirring, soak more than 24h, then turbid solution is poured into centrifuge tube and centrifuged to neutrality, at 80 DEG C after taking-up
12h is dried in vacuum drying oven.The 40mg multi-walled carbon nanotubes of drying and 3mg SDBS are added in 20ml water, ultrasonic disperse 3h, obtained
To carbon nano-tube aqueous solutions.
Step 4：The expanded graphite aqueous solution and carbon nano-tube aqueous solutions are mixed into ultrasonic 30min, uniformly mixed molten
Liquid, add 20ml 0.6 mol/L ZnCl2The aqueous solution, magnetic agitation 4h to uniform mixing；
Step 5：Obtained mixed solution is put into 100 DEG C of drying of convection oven, obtains sample；
Step 6：Be put into after sample is installed with mortar grinder into powder with crucible in tube furnace under ar gas environment, with 5 DEG C/
Min is warming up to 1000 DEG C, and activated sample is made in insulation 2h；
Step 7：By activated sample respectively with 5% salt acid soak, carry out centrifuge washing with a large amount of deionized waters, dry, obtain low
The C-base composte material of warm lithium ion battery.
The C-base composte material of low-temperature lithium ion battery prepared by above-mentioned preparation method is referring to Fig. 2, Fig. 2 is the present invention
The scanning electron microscope (SEM) photograph and transmission electron microscope picture of the C-base composte material of low-temperature lithium ion battery prepared by middle embodiment three, from Fig. 2
In it can be seen that the lamella of graphite all expands, the hole defect of many mesh above lamella be present, CNT intersects
It is supported between graphite flake layer.
Example IV：
Make the battery of the C-base composte material with low-temperature lithium ion battery
The present embodiment is distinguished as with embodiment three：After the completion of step 7, to material and PVDF and the conductive agent obtained
Super p are with 90：5：5 ratio weighs, and adding a small amount of water after grinding uniformly is configured to slurry, and aluminium foil is coated in coating machine
On, it is put into 100 DEG C of vacuum drying oven and is dried in vacuo 12 hours, electrode slice is made, diameter 15mm roundlet is then cut into slitter
Piece, it is about 1 mg cm per tablet quality-2, be then assembled into glove box 2025 button cell, its septation for business every
Film（Celgard 2400）, business 1M LiPF6 mixing EC, DEC (1：1 = v：V, analysis are pure) it is used as electrolyte, lithium paper tinsel conduct
To electrode slice.Finally by the button cell installed using blue electric tester carry out charge-discharge test, respectively 0 degree, -20 spend, -40
Charge-discharge test is carried out under the conditions of degree.
Referring to Fig. 3, Fig. 3 is the C-base composte material group of the low-temperature lithium ion battery prepared by example IV in the present invention
The electro-chemical test figure of the lithium ion battery of dress.As can be seen from Figure 3 the negative material carries out discharge and recharge under cryogenic
Test has excellent charge-discharge performance.
Those of ordinary skill in art it should be appreciated that, the features of the present invention or the first purpose are：
The C-base composte material of low-temperature lithium ion battery prepared by the above method：（1）CNT branch with excellent mechanical properties
Support between the lamella of expanded graphite, prevent the stacking of graphite flake layer, enhance the electric conductivity and stability of structure, accelerate from
The quick transmission of son；（2）The hole of mesh is activated out on graphite flake layer, enables ion vertical transfer, substantially reduces
Transmission path, it is achieved thereby that its high rate capability and cryogenic property as ion cathode material lithium.The lithium-ion electric of assembling
Pond, being capable of normal use at -40 DEG C.
It is complete by above-mentioned description, relevant staff using the above-mentioned desirable embodiment according to the present invention as enlightenment
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to determines its technical scope according to right.
Claims (10)
- A kind of 1. C-base composte material of low-temperature lithium ion battery, it is characterised in that including：Multi-walled carbon nanotube and expansion stone Ink, the expanded graphite are made up of multi-disc graphite flake layer, there is the hole of mesh, the multi-wall carbon nano-tube on every graphite flake layer Pipe is supported between the multi-disc graphite flake layer.
- 2. a kind of preparation method of the C-base composte material of low-temperature lithium ion battery, it is characterised in that including step：(1) weigh expandable powdered graphite to be put into metal enclosed container, it is expanded to be placed in Muffle furnace high temperature, obtains expanding stone Ink；(2) by the expanded graphite ultrasonic disperse in water, the uniform expanded graphite aqueous solution is obtained；(3) multi-walled carbon nanotube ultrasonic disperse is obtained into carbon nano-tube aqueous solutions in water；(4) by the expanded graphite aqueous solution and the carbon nano-tube aqueous solutions ultrasonic mixing it is uniform after, add ZnCl2The aqueous solution, Magnetic agitation obtains mixed solution to uniform mixing；(5) mixed solution is subjected to high temperature drying, sample is made；(6) sample is put into tube furnace under ar gas environment with mortar grinder into powder and carries out high-temperature activation, lived Change sample；(7) activated sample is subjected to centrifuge washing, drying with hydrochloric acid, deionized water respectively, obtains low-temperature lithium ion battery C-base composte material.
- 3. the preparation method of the C-base composte material of low-temperature lithium ion battery according to claim 1, it is characterised in that：Step Suddenly the quality of expandable powdered graphite described in (1) is 1 ~ 2g, and the temperature in the Muffle furnace is 950-1050 DEG C, the height Warm puffing time is 28-32s.
- 4. the preparation method of the C-base composte material of low-temperature lithium ion battery according to claim 1, it is characterised in that：Step Suddenly the quality of expanded graphite described in (2) is 0.7-1g, and the volume of the water is 40-60ml, in step (2), in ultrasonic disperse When add PEGMO, the addition of the PEGMO is 1-3ml.
- 5. the preparation method of the C-base composte material of low-temperature lithium ion battery according to claim 1, it is characterised in that：Step Suddenly the quality of multi-walled carbon nanotube described in (3) is 20-40mg, and the volume of the water is 20-50ml, the multi-walled carbon nanotube A diameter of 20-40nm.
- 6. the preparation method of the C-base composte material of low-temperature lithium ion battery according to claim 1, it is characterised in that：Step Suddenly in (3) before ultrasonic disperse, SDBS is added in water, the addition of the SDBS is 2-4mg.
- 7. the preparation method of the C-base composte material of low-temperature lithium ion battery according to claim 1, it is characterised in that：Step Suddenly the mol/L of 18-22ml 0.6 ZnCl is added in (4)2The aqueous solution, the ultrasonic mixing time are 28-32min, the magnetic force Mixing time is 3-5h.
- 8. the preparation method of the C-base composte material of low-temperature lithium ion battery according to claim 1, it is characterised in that：Step Suddenly high temperature drying is described in (5)：The forced air drying 9-12h under the conditions of 90-110 DEG C.
- 9. the preparation method of the C-base composte material of low-temperature lithium ion battery according to claim 1, it is characterised in that：Step Suddenly the temperature of high-temperature activation described in (6) is 950-1050 DEG C, time 1-3h.
- 10. the preparation method of the C-base composte material of low-temperature lithium ion battery according to claim 1, it is characterised in that： Concentration of hydrochloric acid described in step (7) is 5%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585832A (en) * | 2018-12-05 | 2019-04-05 | 中南大学 | A kind of sulfur doping micro crystal graphite and preparation method thereof and application as anode material of lithium-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 |
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| CN106025297A (en) * | 2016-07-29 | 2016-10-12 | 盐城工学院 | Electrode preparation method of new energy source automobile fuel cell |
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| CN109585832A (en) * | 2018-12-05 | 2019-04-05 | 中南大学 | A kind of sulfur doping micro crystal graphite and preparation method thereof and application as anode material of lithium-ion battery |
| 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 |
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