CN108807903A - A kind of preparation method of the composite modified lithium cell cathode material of lithium battery - Google Patents
A kind of preparation method of the composite modified lithium cell cathode material of lithium battery Download PDFInfo
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- CN108807903A CN108807903A CN201810600163.1A CN201810600163A CN108807903A CN 108807903 A CN108807903 A CN 108807903A CN 201810600163 A CN201810600163 A CN 201810600163A CN 108807903 A CN108807903 A CN 108807903A
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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
- H01M4/366—Composites as layered products
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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 technical field of lithium ion battery electrode, and in particular to a kind of lithium battery preparation method of composite modified lithium cell cathode material includes the following steps：By mass ratio (1~2)：1 graphene and carbon nanotube are put into solvent, and after being handled by ultrasonic preliminary crushing, it is mixed 4~6 minutes at normal temperatures, then 40~60 DEG C are warming up to the speed of 2~4 DEG C/min in the environment of inert gas shielding, 4~6h is kept the temperature again, then cooled to room temperature, obtain mixed solution, so, in the application, it is that carbon nanotubes and graphene are subjected to moditied processing first, utilize the high conductivity of graphene and carbon nanotube, graphene is multi-layer graphene, the inside of multi-layer graphene is in 3 D stereo conductive network structure, and then promote migration velocity of the lithium electronics in clad.
Description
Technical field：
The present invention relates to technical field of lithium ion battery electrode, and in particular to a kind of lithium battery composite modified lithium electricity
The preparation method of pond negative material.
Background technology：
Lithium battery is one kind using lithium metal or lithium alloy as negative material, using the one-shot battery of non-aqueous electrolytic solution,
With lithium ion polymer battery it is different with rechargeable battery lithium ion battery.The inventor of lithium battery is Edison.By
It is very active in the chemical characteristic of lithium metal so that processing, preservation, the use of lithium metal, it is very high to environmental requirement.So
Lithium battery is not applied for a long time.With the development of twentieth century end microelectric technique, the equipment of miniaturization is increasing, right
Power supply proposes very high requirement.Lithium battery enters the large-scale practical stage therewith.Ferric phosphate lithium anode reacts：Electric discharge
When lithium ion be embedded in, lithium ion deintercalation when charging.When charging：When LiFePO4 → Li1-xFePO4+xLi++xe- discharges：Li1-
XFePO4+xLi++xe- → LiFePO4 cathode, negative material：Mostly use graphite.New research finds that titanate may be more preferable
Material.Negative reaction：Lithium ion is de- when electric discharge inserts, and lithium ion is inserted into when charging.When charging：XLi++xe-+6C → LixC6 is put
When electric：LixC6→xLi++xe-+6C.
Negative material is one of critical material of lithium ion battery, and the lithium ion battery negative material used is commercialized at present
Mainly charcoal class negative material.It has height ratio capacity (200~400mAh/g), low electrode current potential (< 1.0Vvs Li+/Li),
The advantages that high circulation efficiency (> 95%) and long circulation life.There are carbonaceous mesophase spherules (MCMB), stone in charcoal class negative material
Ink and amorphous carbon, wherein graphite has good layer structure, reversible specific capacity can because its good conductivity, crystallinity are high
A kind of ultrafine graphite cathode material is invented up to 300mah/g or more, Chen et al., the auxiliary material after being produced using high-end graphite
It for the primary raw material of the product, on the basis of making particle size reduction to 5um by attritioning, then is surface-treated, is carbonized by 1200 °
Afterwards, then 3000 ° of graphitization sintering are carried out, then carries out coarse crushing sieving and acquires corresponding product, there is this product good conduction to make
With resistance is low, and processing performance is good in lithium ion battery production process, and performance is stablized, cost-effective, is rate lithium battery
Best negative material.But the disadvantage is that graphite material structural stability is poor, the poor compatibility with electrolyte, and Li ions have at it
Diffusion velocity in sequence layer structure is slow, and the material is caused to be unable to high rate charge-discharge.And soft carbon crystallinity is low, crystallite dimension
Small, interplanar distance is big, good with compatibility of electrolyte, but first charge-discharge irreversible capacity is preferable, and application range is smaller, to above
Some faults of construction of artificial graphite as lithium ion battery negative material itself, in order to obtain the cathode material of high electrochemical performance
Material, it is necessary to the modification and modification on a deep step surface are carried out to it.
Invention content：
The present invention overcomes the deficiencies of existing technologies, and provides that a kind of first charge-discharge efficiency is high, specific capacity is high, solves existing
The carbon problem that existing irreversible capacity loss is big when actually preparing the application of cathode of lithium battery, specific capacity is relatively low in technology.
The technical problems to be solved by the invention are realized using technical solution below：A kind of lithium battery is with composite modified
The preparation method of lithium cell cathode material, includes the following steps：
(1) by mass ratio (1~2)：1 graphene and carbon nanotube are put into solvent, and by ultrasonic preliminary crushing at
After reason, it is mixed 4~6 minutes at normal temperatures, then with the speed liter of 2~4 DEG C/min in the environment of inert gas shielding
Temperature is to 40~60 DEG C, then keeps the temperature 4~6h, then cooled to room temperature, obtains mixed solution；
(2) use asphalt for base-material, it is 120~140um which, which is crushed with ball-milling treatment to grain size, then
Will treated that particle puts into that processing is modified into reaction kettle, step includes：
(2.1) it uses flow velocity to be passed through nitrogen for 80~120 air speeds hourly, then carries out being warming up to 300~420 DEG C,
Heating rate is 40~60 DEG C/h, keeps the temperature 2~6h；
(2.2) pitch in part steps (2.1) is taken to be crushed to grain size in 20um hereinafter, and measure softening point, and herein
At a temperature of keep the temperature 4~6h, until the asphalt base-material of the softening point that measures at 180~380 DEG C；
(2.3) by the asphalt base-material cooled to room temperature in step (2.2), the light base-material of Lee, which is then crushed to grain size, is
18~20um, as modified pitch base-material；
(3) pitch obtained in step (2) sieve base-material is dissolved in the tetrahydrofuran solution that pitch is obtained in tetrahydrofuran,
And pour into the tetrahydrofuran solution of the pitch of preparation in mixed solution, 20~40min is stirred, mixed slurry is obtained, is then added
Enter the solid masses percentage composition of solvent adjustment mixed slurry to 10~20%；
(4) mixed slurry in step (3) is dried by closed cycle spray drying machine, closed cycle spray is dry
The inlet temperature and outlet temperature of dry machine are respectively 120~140 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine
Rotating speed be 24000~26000r/min, formed presoma；
(5) presoma in the step (4) is put into atomizer, using presoma：The volume ratio of solvent is 1：30
~35 ratio mixes and is formed spray, and is warming up to 500~700 DEG C in the state that protective gas is protected and carries out at annealing
Then reason is loaded into 24~26% gaseous carbon source, 50~1000ml/min of gas flow rate by protective gas, while opening atomization
Device, protective gas take the tiny ingredient being atomized in atomizer in high temperature furnace to, keep the temperature 1~12 hour, make the gaseous carbon source
It cracks to form amorphous carbon on presoma surface, which is coated on the surface of presoma and forms uniform clad,
Obtain the lithium cell cathode material.
The solvent is at least one of distilled water, methanol, ethyl alcohol, ethylene glycol, ether, acetone.
Graphene described in the step (1) is multi-layer graphene, and the inside of the multi-layer graphene is in 3 D stereo
Conductive network structure, the carbon nanotube are inserted in the 3 D stereo conductive network, multi-layer graphene and carbon nanotube effect
The grain diameter formed afterwards is 700nm~22um.
The ratio between parts by weight of graphene, the parts by weight of carbon nanotube and solvent are 1 in the step (1)：1~1：5.
In the application, processing is modified to asphalt, is carried out for the oxidation reaction system of current existing pitch
Optimization, i.e., remove volatile light component, then carry out low-temperature oxidation reaction, in high temperature first with inert atmosphere at high temperature
When, the oxidation reaction of pitch is exothermic reaction, therefore in theory, and relative low temperature is advantageous for the oxidation polymerization of pitch
, and energy consumption can be reduced.And this exothermic effect is not accounted in the method for promoting asphalt softening point existing at present, only one
The heated asphalt prolonged at high temperature of taste is allowed to that the separation of light component side occurs, and side polymerisation, modified pitch has
The high advantage of softening point so that pitch can faster carry out carburizing reagent with graphene and carbon nanotubes, so as to
Structure enough between guarantee graphene and carbon nanotubes coats agraphitic carbon simultaneously, in periphery, has so both improved the steady of structure
It is qualitative, carbon nanotubes and graphene-structured are protected, and shorten the reaction time.
The application is that carbon nanotubes and graphene are carried out moditied processing, profit first in the application compared with prior art
With the high conductivity of graphene and carbon nanotube, graphene is multi-layer graphene, and the inside of multi-layer graphene is led in 3 D stereo
Electric network structure, and then migration velocity of the lithium electronics in clad is promoted, carbon nanotube, which is inserted, is embedded in the 3 D stereo conductive mesh
In network, the grain diameter formed after multi-layer graphene and carbon nanotube effect is 700nm~22um, which is mixed at normal temperatures
Stirring 4~6 minutes is closed, is then warming up to 40~60 DEG C in the environment of inert gas shielding with the speed of 2~4 DEG C/min, then
4~6h is kept the temperature, then cooled to room temperature, obtains mixed solution, can further drain multi-layer graphene and nanometer in this way
Micro-bubble between carbon pipe forms stable binder course, is conducive to preferably play graphene and the conduction of carbon nanotube is special
Property, then prepare presoma using the mode that closed cycle spray is dried, modified pitch it is evenly dispersed on the surface of graphene on, warp
After crossing high-temperature heat treatment, one layer of unbodied charcoal is formed after asphalt carbonization, is tightly wrapped in graphene surface, is formed a kind of
The composite material of " core-shell " structure, the presence of clad not only reduce the specific surface area of material, prevent organic solvent
Into, achieve the purpose that obtain SEI films uniformly, fine and close, meanwhile, surface Carbon Materials can fix graphite flake, prevent graphite surface layer
Fall off so that first charge discharge efficiency, specific capacity and the cyclical stability of material obtain certain raising, finally use in protective gas
It is warming up to 500~700 DEG C in the state of protection to be made annealing treatment, which can further promote carbon nanotubes and stone
Stability between black alkene so that the negative material stability for preparing formation is strong, is then loaded into 24~26% by protective gas
Gaseous carbon source, 50~1000ml/min of gas flow rate, while opening atomizer, protective gas is tiny by what is be atomized in atomizer
Ingredient takes in high temperature furnace, keeps the temperature 1~12 hour, the gaseous carbon source is made to crack to form amorphous carbon on presoma surface, should
Agraphitic carbon is coated on the surface of presoma and forms uniform clad, obtains the lithium cell cathode material, packet at this time
Coating cracks to be formed by gaseous carbon source, and it is de- on negative material surface that double-deck clad can advantageously reduce lithium ion
Go out the polarization resistance with telescopiny, improves the high rate performance of lithium cell cathode material of the present invention, double-deck clad being capable of stone
Ink material structural stability is poor, the poor compatibility with electrolyte, and diffusion velocity of the Li ions in its ordered lamellar structure is slow
The problem of.
Specific implementation mode：
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1：
A kind of lithium battery preparation method of composite modified lithium cell cathode material, includes the following steps：
(1) by mass ratio 1：1 graphene and carbon nanotube are put into solvent, and by ultrasonic preliminary crushing handle after,
It is mixed 4~6 minutes at normal temperatures, is then warming up to 40 in the environment of inert gas shielding with the speed of 2~4 DEG C/min
~60 DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed solution；
(2) use asphalt for base-material, it is 120~140um which, which is crushed with ball-milling treatment to grain size, then
Will treated that particle puts into that processing is modified into reaction kettle, step includes：
(2.1) it uses flow velocity to be passed through nitrogen for 80~120 air speeds hourly, then carries out being warming up to 300~420 DEG C,
Heating rate is 40~60 DEG C/h, keeps the temperature 2~6h；
(2.2) pitch in part steps (2.1) is taken to be crushed to grain size in 20um hereinafter, and measure softening point, and herein
At a temperature of keep the temperature 4~6h, until the asphalt base-material of the softening point that measures at 180~380 DEG C；
(2.3) by the asphalt base-material cooled to room temperature in step (2.2), the light base-material of Lee, which is then crushed to grain size, is
18~20um, as modified pitch base-material；
(3) pitch obtained in step (2) sieve base-material is dissolved in the tetrahydrofuran solution that pitch is obtained in tetrahydrofuran,
And pour into the tetrahydrofuran solution of the pitch of preparation in mixed solution, 20~40min is stirred, mixed slurry is obtained, is then added
Enter the solid masses percentage composition of solvent adjustment mixed slurry to 10~20%；
(4) mixed slurry in step (3) is dried by closed cycle spray drying machine, closed cycle spray is dry
The inlet temperature and outlet temperature of dry machine are respectively 120~140 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine
Rotating speed be 24000~26000r/min, formed presoma；
(5) presoma in the step (4) is put into atomizer, using presoma：The volume ratio of solvent is 1：30
~35 ratio mixes and is formed spray, and is warming up to 500~700 DEG C in the state that protective gas is protected and carries out at annealing
Then reason is loaded into 25% gaseous carbon source, 50~1000ml/min of gas flow rate by protective gas, while opening atomizer, protect
Shield gas takes the tiny ingredient being atomized in atomizer in high temperature furnace to, keeps the temperature 1~12 hour, makes the gaseous carbon source in forerunner
Body surface facial cleft solution forms amorphous carbon, which is coated on the surface of presoma and forms uniform clad, obtains institute
State lithium cell cathode material.
The solvent is acetone.
Graphene described in the step (1) is multi-layer graphene, and the inside of the multi-layer graphene is in 3 D stereo
Conductive network structure, the carbon nanotube are inserted in the 3 D stereo conductive network, multi-layer graphene and carbon nanotube effect
The grain diameter formed afterwards is 700nm~22um.
The ratio between parts by weight of graphene, the parts by weight of carbon nanotube and solvent are 1 in the step (1)：1~1：5.
Embodiment 2：
The present embodiment content and 1 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
Step (1) is by mass ratio 1.5：1 graphene and carbon nanotube are put into solvent, and by ultrasonic preliminary crushing handle after,
It is mixed 4~6 minutes under room temperature, then 40 are warming up to the speed of 2~4 DEG C/min in the environment of inert gas shielding~
60 DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed solution.
Embodiment 3：
The present embodiment content and 1 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
Step (1) is by mass ratio 2：1 graphene and carbon nanotube are put into solvent, and by ultrasonic preliminary crushing handle after, normal
Temperature is lower to be mixed 4~6 minutes, is then warming up to 40~60 in the environment of inert gas shielding with the speed of 2~4 DEG C/min
DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed solution.
Embodiment 4：
The present embodiment content and 2 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
Step (5) puts into the presoma in the step (4) in atomizer, using presoma：The volume ratio of solvent is 1：30~35
Ratio mix and formed spray, and be warming up to 500~700 DEG C in the state that protective gas is protected and made annealing treatment, so
24% gaseous carbon source, 50~1000ml/min of gas flow rate are loaded by protective gas afterwards, while opening atomizer, protective gas
The tiny ingredient being atomized in atomizer is taken in high temperature furnace, 1~12 hour is kept the temperature, makes the gaseous carbon source on presoma surface
Cracking forms amorphous carbon, which is coated on the surface of presoma and forms uniform clad, obtains the lithium electricity
Pond negative material.
Embodiment 5：
The present embodiment content and 2 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
Step (5) puts into the presoma in the step (4) in atomizer, using presoma：The volume ratio of solvent is 1：30~35
Ratio mix and formed spray, and be warming up to 500~700 DEG C in the state that protective gas is protected and made annealing treatment, so
26% gaseous carbon source, 50~1000ml/min of gas flow rate are loaded by protective gas afterwards, while opening atomizer, protective gas
The tiny ingredient being atomized in atomizer is taken in high temperature furnace, 1~12 hour is kept the temperature, makes the gaseous carbon source on presoma surface
Cracking forms amorphous carbon, which is coated on the surface of presoma and forms uniform clad, obtains the lithium electricity
Pond negative material.
Comparative example 1：
This comparative example and 2 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that, the step
(1) by mass ratio 0.5：1 graphene and carbon nanotube are put into solvent, and by ultrasonic preliminary crushing handle after, in room temperature
It is lower to be mixed 4~6 minutes, then 40~60 are warming up to the speed of 2~4 DEG C/min in the environment of inert gas shielding
DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed solution.
Comparative example 2：
This comparative example and 2 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that, the step
(1) by mass ratio 3：1 graphene and carbon nanotube are put into solvent, and by ultrasonic preliminary crushing handle after, at normal temperatures
It is mixed 4~6 minutes, is then warming up to 40~60 DEG C in the environment of inert gas shielding with the speed of 2~4 DEG C/min,
4~6h is kept the temperature again, then cooled to room temperature, obtain mixed solution.
Comparative example 3：
This comparative example and 2 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that, the step
(5) presoma in the step (4) is put into atomizer, using presoma：The volume ratio of solvent is 1：30~35 ratio
Example, which mixes, simultaneously forms spray, and is warming up to 500~700 DEG C in the state that protective gas is protected and is made annealing treatment, then by
Protective gas is loaded into 22% gaseous carbon source, 50~1000ml/min of gas flow rate, while opening atomizer, and protective gas is by mist
Change the tiny ingredient being atomized in device to take in high temperature furnace, keep the temperature 1~12 hour, the gaseous carbon source is made to be cracked on presoma surface
Amorphous carbon is formed, which is coated on the surface of presoma and forms uniform clad, and it is negative to obtain the lithium battery
Pole material.
Comparative example 4：
This comparative example and 2 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that, the step
(5) presoma in the step (4) is put into atomizer, using presoma：The volume ratio of solvent is 1：30~35 ratio
Example, which mixes, simultaneously forms spray, and is warming up to 500~700 DEG C in the state that protective gas is protected and is made annealing treatment, then by
Protective gas is loaded into 28% gaseous carbon source, 50~1000ml/min of gas flow rate, while opening atomizer, and protective gas is by mist
Change the tiny ingredient being atomized in device to take in high temperature furnace, keep the temperature 1~12 hour, the gaseous carbon source is made to be cracked on presoma surface
Amorphous carbon is formed, which is coated on the surface of presoma and forms uniform clad, and it is negative to obtain the lithium battery
Pole material.
Comparative example 5：
This comparative example selects a kind of hollow porous carbon/silicon nanometer of doped graphene disclosed in CN201510545414.7
Fiber lithium cell cathode material prepares to form the cathode of lithium battery.
Paste glue is made in negative material and butadiene-styrene rubber, aqueous binder that Examples 1 to 5, comparative example 1~5 obtain
Mixture, even application is cut in copper foil both sides, roll-in, at negative plate；It is assembled for lithium battery, tests its 10C charge/discharge capacity
Conservation rate, for the first time discharge capacity, for the first time coulombic efficiency.Obtained data are as shown in table 1.
Table 1
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (4)
1. a kind of lithium battery preparation method of composite modified lithium cell cathode material, which is characterized in that include the following steps：
(1) by mass ratio (1~2)：1 graphene and carbon nanotube are put into solvent, and by ultrasonic preliminary crushing handle after,
It is mixed 4~6 minutes at normal temperatures, is then warming up to 40 in the environment of inert gas shielding with the speed of 2~4 DEG C/min
~60 DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed solution；
(2) use asphalt for base-material, it is 120~140um which, which is crushed with ball-milling treatment to grain size, then will place
Particle after reason, which is put into, is modified processing into reaction kettle, and step includes：
(2.1) it uses flow velocity to be passed through nitrogen for 80~120 air speeds hourly, then carries out being warming up to 300~420 DEG C, heating
Speed is 40~60 DEG C/h, keeps the temperature 2~6h；
(2.2) pitch in part steps (2.1) is taken to be crushed to grain size in 20um hereinafter, and measure softening point, and in this temperature
4~6h of lower heat preservation, until asphalt base-material of the softening point measured at 180~380 DEG C；
(2.3) by the asphalt base-material cooled to room temperature in step (2.2), then by the light base-material of Lee be crushed to grain size be 18~
20um, as modified pitch base-material；
(3) pitch obtained in step (2) sieve base-material is dissolved in the tetrahydrofuran solution that pitch is obtained in tetrahydrofuran, and will
The tetrahydrofuran solution of the pitch of preparation pours into mixed solution, stirs 20~40min, obtains mixed slurry, be then added molten
Agent adjusts the solid masses percentage composition of mixed slurry to 10~20%；
(4) mixed slurry in step (3) is dried by closed cycle spray drying machine, closed cycle spray drying machine
Inlet temperature and outlet temperature be respectively 120~140 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine turns
Speed is 24000~26000r/min, forms presoma；
(5) presoma in the step (4) is put into atomizer, using presoma：The volume ratio of solvent is 1：30~35
Ratio mix and formed spray, and be warming up to 500~700 DEG C in the state that protective gas is protected and made annealing treatment, so
24~26% gaseous carbon source, 50~1000ml/min of gas flow rate are loaded by protective gas afterwards, while opening atomizer, is protected
Gas takes the tiny ingredient being atomized in atomizer in high temperature furnace to, keeps the temperature 1~12 hour, makes the gaseous carbon source in presoma
Surface cracks to form amorphous carbon, which is coated on the surface of presoma and forms uniform clad, obtains described
Lithium cell cathode material.
2. the lithium battery according to claim 1 preparation method of modified phosphate iron lithium anode material, which is characterized in that institute
The solvent stated is at least one of distilled water, methanol, ethyl alcohol, ethylene glycol, ether, acetone.
3. the lithium battery according to claim 1 preparation method of modified phosphate iron lithium anode material, which is characterized in that institute
Graphene described in the step of stating (1) is multi-layer graphene, and the inside of the multi-layer graphene is in 3 D stereo conductive network knot
Structure, the carbon nanotube are inserted in the 3 D stereo conductive network, formed after multi-layer graphene and carbon nanotube effect
Grain grain size is 700nm~22um.
4. the lithium battery according to claim 1 preparation method of modified phosphate iron lithium anode material, which is characterized in that institute
It is 1 to state the ratio between parts by weight of graphene, the parts by weight of carbon nanotube and solvent in step (1)：1~1：5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111554898A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Negative electrode material and preparation method and application thereof |
| CN111785915A (en) * | 2020-07-27 | 2020-10-16 | 湖南中科星城石墨有限公司 | Low-crystallization-degree coating material and preparation method thereof, negative electrode material and lithium battery negative electrode |
| CN111785915B (en) * | 2020-07-27 | 2022-04-01 | 湖南中科星城石墨有限公司 | Low-crystallization-degree coating material and preparation method thereof, negative electrode material and lithium battery negative electrode |
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