CN105336953B - A kind of preparation method of the graphitized intermediate-phase carbosphere negative material of surface controllable oxidization - Google Patents
A kind of preparation method of the graphitized intermediate-phase carbosphere negative material of surface controllable oxidization Download PDFInfo
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- CN105336953B CN105336953B CN201510639980.4A CN201510639980A CN105336953B CN 105336953 B CN105336953 B CN 105336953B CN 201510639980 A CN201510639980 A CN 201510639980A CN 105336953 B CN105336953 B CN 105336953B
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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
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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 invention discloses a kind of preparation method of the graphitized intermediate-phase carbosphere negative material of surface controllable oxidization, comprise the following steps：1）Measure sulfuric acid and nitric acid, one or more mixing of perchloric acid, phosphoric acid, ultrasound or the stirring certain time of certain volume；2）A certain amount of graphitized intermediate-phase carbosphere is added in nitration mixture, ultrasound or mechanical agitation certain time；3）A certain amount of chromium trioxide is added in above-mentioned mixed liquor, the regular hour is aoxidized under ultrasound or stirring condition, after question response terminates, filtering obtains black solid；4）After filtering, certain density hydrochloric acid and distilled water washes clean repeatedly, drying are used；5）The solid of drying is placed in tube furnace the high-temperature heat treatment certain time under protective atmosphere and is cooled to room temperature.There is relatively low removal lithium embedded platform, higher platform capacity using the graphitized intermediate-phase carbosphere of surface controllable oxidization made of technical solution of the present invention.Meanwhile there is good degree of graphitization and excellent cycle performance.
Description
Technical field
The present invention relates to a kind of preparation method of lithium cell cathode material, more particularly to a kind of graphite of surface controllable oxidization
Change the preparation method of intermediate phase carbon microsphere negative materials.
Background technology
Important component of the lithium ion battery as electronic product, makes it play increasingly in the life of people
Important role.In recent years, because electric automobile and hybrid-electric car are fast-developing so that people are highly desirable to develop
The battery of the power-type lithium ion of height ratio capacity and high-energy-density.The research of lithium ion battery negative material is for power type lithium
The research and development of the battery of ion are most important.High-performance negative material must meet two big basic demands first：（1）With relatively low
Oxidation-reduction potential platform, make battery that there is higher output voltage；（2）It is embedded in and deviates from lithium ion as much as possible, makes electricity
Pond has high specific capacity and energy density.Currently, commercialized ion cathode material lithium is mainly based on graphite type material.
Graphite has special layer structure, is connected between layer and is connected with weaker Van der Waals force, interlamellar spacing 0.3354nm.It is this to have
The structure of profit enables the interlayer that lithium ion is embedded in graphite to form compound between graphite layers without destroying its structure.Lithium ion
Can be under relatively low potential（0.01~0.25V）It is embedded into graphite layers, and is somebody's turn to do " low embedding lithium potential " and is to ensure that battery is " high defeated
Go out voltage " basic premise.However, the theoretical specific capacity of graphite cathode material is only 372mAh/g, it can not yet reach high
The requirement of performance negative material.
In numerous graphite materials, graphitized intermediate-phase carbon microballoon（GMCMB）Get the attention and highly recognition.With
Conventional graphite material is compared, and GMCMB also has two big advantages：（1）Spherical structure can realize the tightly packed of material, can prepare
High-density electrode；（2）Spherome surface is smooth, and specific surface area is low, reduces the generation of side reaction, improves first charge-discharge effect
Rate.Above-mentioned advantage makes GMCMB become a kind of negative material of great application prospect.Nevertheless, GMCMB in actual applications
Still suffer from the not high enough bottleneck problem of specific capacity.Therefore, modification is implemented to GMCMB, improves its specific capacity to meet
Power lithium-ion battery requirement, just like a very important Task.At present, the side that a kind of effective GMCMB is modified
Method is " oxidationreduction " processing, i.e., by chemical oxidation, surface oxidation modification is carried out to GMCMB, purpose improves GMCMB electricity
Chemical property.Such as GMCMB is placed in ammonia atmosphere by Han et al., reaction temperature is 800 DEG C, is successfully prepared nitrating
GMCMB。
The content of the invention
Although oxidation processes can be modified GMCMB, easily there is the phenomenon of over oxidation.Due to excessive oxygen
Change, the spherical structure of carbonaceous mesophase spherules is destroyed, and bulk density reduces, and degree of graphitization reduces, and is led when as negative pole
Electrically reduce, cycle performance declines.
The present invention carries out surface modification by controllable oxidization system to GMCMB, it is intended to keeps GMCMB spherical structures and original
While having crystallinity, its specific capacity and cycle performance are improved.Using a variety of means of testing to modified GMCMB negative pole materials
Material is analyzed, and inquires into the correlation of method of modifying and pattern, structure and chemical property.
The content of the invention
The invention aims to improve the specific capacity and cyclical stability of graphitized intermediate-phase carbosphere, there is provided
A kind of preparation method of the graphitized intermediate-phase carbosphere negative material of surface controllable oxidization.The main process of this method is to stone
The mixed liquor of inkization carbonaceous mesophase spherules and sulfuric acid, nitric acid, phosphoric acid etc. carries out ultrasound, then using chromium trioxide in graphitization
Between phase carbosphere aoxidized, make graphitized intermediate-phase carbosphere can keep spherical structure and can improve surface topography.Surface
On the one hand controllable oxidization keeps the spherical structure of graphitized intermediate-phase carbosphere, it is ensured that the bulk density of material, on the other hand may be used
To increase the storage lithium site on graphitized intermediate-phase carbosphere surface, the specific capacity of material is improved.Controllable oxidization graphitized intermediate-phase
Carbosphere（EMCMB）The spherical structure of carbosphere and original degree of graphitization can be kept, and can increases the specific volume of carbosphere
Amount and cycle performance.
A kind of the technical scheme is that graphitized intermediate-phase carbosphere lithium cell cathode material of surface controllable oxidization
Preparation method.This method comprises the steps：
1）Sulfuric acid and nitric acid, the one or more mixing of perchloric acid, phosphoric acid of certain volume are measured, ultrasound or stirring are certain
Time；
2）A certain amount of graphitized intermediate-phase carbosphere is added in nitration mixture, ultrasound or mechanical agitation regular hour；
3）A certain amount of chromium trioxide is added in above-mentioned mixed liquor, when aoxidizing certain under ultrasound or stirring condition
Between, after question response terminates, room temperature is cooled to, filtering obtains black solid；
4）After solid filtering, certain density hydrochloric acid and distilled water washes clean repeatedly, drying are used；
5）The solid of drying is placed in tube furnace the high-temperature heat treatment regular hour under protective atmosphere and quickly cooled down
To room temperature.
In step 1）In, sulfuric acid dosage is 50 ~ 200mL, nitric acid dosage is 20 ~ 200mL, perchloric acid is 20 ~ 200mL, phosphorus
Acid is 20 ~ 200mL, and nitration mixture is that sulfuric acid mixes with the one or more of nitric acid, perchloric acid, phosphoric acid, ultrasonic time for 10 ~
120min, ultrasonic power 40-300W, ultrasonic temperature are 20 ~ 100 DEG C, or during use agitating mode mixing, mixing time 10
~ 120min, stir speed (S.S.) are 100 ~ 2000r/min.
In step 2）In, the dosage of graphitized intermediate-phase carbosphere is 1 ~ 20g, and ultrasonic time is 10 ~ 120min, ultrasonic work(
Rate is 40-300W, and ultrasonic temperature is 20 ~ 100 DEG C, or during use agitating mode mixing, mixing time is 10 ~ 120min, stirring
Speed is 100 ~ 2000r/min.
In step 3）In, the dosage of chromium trioxide is 1 ~ 50g, and the temperature control of oxidation is at 20 ~ 100 DEG C, the time of oxidation
For 1 ~ 48h.
In step 4）In, the concentration of hydrochloric acid solution is 1 ~ 20%.
In step 5）In, the protective atmosphere of the heat treatment is argon gas, nitrogen, helium, one kind of hydrogen or its person mixing
Gas, gas flow is 50~300mL/min, with 1~20 DEG C/min heating rate from room temperature to 600~1200 DEG C,
Soaking time is 10 ~ 120min, fast cooling to room temperature.The heat treatment mode includes microwave heating or arc process heating.
Advantages of the present invention：The graphitized intermediate-phase carbosphere carbon-coating of surface controllable oxidization is softened, and surface has piece
Rotating fields, the immersion of electrolyte and the transmission of ion can be promoted.Surface controllable oxidization enters to graphitized intermediate-phase carbosphere
The oxidation processes on row surface, the spherical destruction that over oxidation causes graphitized intermediate-phase carbosphere is avoided, crystallinity declines, interior
The problems such as resistance increase.On the one hand the spherical structure of graphitized intermediate-phase carbosphere is kept, it is ensured that the bulk density of material, the opposing party
Face can increase the storage lithium site on graphitized intermediate-phase carbosphere surface, improve the specific capacity of material.The stone of surface controllable oxidization
Inkization carbonaceous mesophase spherules have relatively low removal lithium embedded platform, higher platform capacity.Meanwhile with the original graphitization of holding
Degree and excellent cycle performance.
Brief description of the drawings
Fig. 1 is the SEM photograph of the graphitized intermediate-phase carbosphere of the controllable oxidization of the present invention；
Fig. 2 is the graphitized intermediate-phase carbosphere of the graphitized intermediate-phase carbosphere raw material that the present invention uses and controllable oxidization
XRD；
Fig. 3 is the graphitized intermediate-phase carbosphere of the graphitized intermediate-phase carbosphere raw material that the present invention uses and controllable oxidization
Charging and discharging curve figure；
Fig. 4 is the graphitized intermediate-phase carbosphere of the graphitized intermediate-phase carbosphere raw material that the present invention uses and controllable oxidization
Cycle performance figure；
Fig. 5 is the graphitized intermediate-phase carbosphere of the graphitized intermediate-phase carbosphere raw material that the present invention uses and controllable oxidization
High rate performance figure.
Embodiment
Embodiment 1
150mL H are measured respectively2SO4With 180 mL HNO3It is placed in the round-bottomed flask that volume is 500 mL, stirs 5min
Mix.8g graphitized intermediate-phase carbospheres are weighed, are added in mixed acid, ultrasonic 20min.Then toward adding 3g in mixed liquor
CrO3, 7h is stirred at a temperature of 40 DEG C.After question response terminates, room temperature is cooled to, filtering obtains black solid.Use 5% salt
Acid solution cleans five times, is then washed repeatedly to neutrality with distilled water, and in vacuum environment, dried at a temperature of 80 DEG C.So
Dry black solid is placed in quartz tube furnace afterwards.Be passed through argon gas as protection gas, gas flow 100mL/min, with
10oC/min heating rate is incubated 10min from room temperature to 800 DEG C, fast cooling is then carried out to room temperature, so as to obtain
Burning forging product.Obtained calcined product is collected, it is standby.
The pattern of graphitization mesocarbon microbeads prepared by controllable oxidization is as shown in Figure 1.Fig. 1（a）For controlled oxygen under low range
The electron microscope of the graphitization mesocarbon microbeads of change, it can be seen that after controllable oxidization, carbonaceous mesophase spherules are still protected
Hold spherical structure.Fig. 1（b）It is obvious from figure for the electron microscope of the graphitization mesocarbon microbeads of controllable oxidization under high magnification
Find out, graphitized intermediate-phase carbosphere obtains appropriate oxidation, and it keeps spherical structure, and graphite linings are slightly strutted, and surface goes out
Some existing cracks and the structure of lamella.
The graphitization mesocarbon microbeads that it can be seen from Fig. 2 XRD data prepared by controllable oxidization remain good knot
Brilliant degree.
With the graphitization mesocarbon microbeads of obtained controllable oxidization, binding agent（PVDF）, conductive carbon black（SP）Quality
Than for 80:10:10, coated on negative pole is used as in copper foil, using metal lithium sheet as to electrode, are assembled into button cell.Electrolyte
It is 1 that the electrolyte formed as 1 mole of hexafluoro phosphorus lithium, which is dissolved in volume ratio,:1 ethylene carbonate and the mixed solvent of propene carbonate
In.Button cell is tested under 100mA/g current density.
As seen from Figure 3, the graphitization mesocarbon microbeads of controllable oxidization and used graphitized intermediate-phase carbosphere
Equally（In addition to discharge curve first）, there is relatively low embedding lithium platform.Controlled oxygen is can be seen that with reference to the discharge and recharge data of table 1
The graphitization mesocarbon microbeads of change have higher specific capacity, coulomb compared with used graphitized intermediate-phase carbosphere
Efficiency is also close with used graphitized intermediate-phase carbosphere, and it is micro- to illustrate that surface controllable oxidization can improve graphitization middle carbon
The specific capacity of ball.
The graphitized intermediate-phase carbosphere raw material and the graphitized intermediate-phase carbosphere of controllable oxidization that table 1 uses for the present invention
First, second and the 5th discharge and recharge tables of data.
From fig. 4, it can be seen that graphitized intermediate-phase carbon used in the graphited mesocarbon microbeads ratio of controllable oxidization is micro-
The specific capacity of ball is high, when the graphited mesocarbon microbeads of controllable oxidization are as negative material, has good cycle performance, passes through
The specific capacity for crossing the graphited mesocarbon microbeads of controllable oxidization after circulating 50 times still reaches 661mAh/g.
From fig. 5, it can be seen that specific capacity of the graphitization mesocarbon microbeads of controllable oxidization under different multiplying powers is than institute
The height of the graphitized intermediate-phase carbosphere used.After different circulations, the graphitization mesocarbon microbeads of controllable oxidization,
Under 100mA/g current density, specific capacity reaches 646mAh/g, shows excellent invertibity.
Embodiment 2
130mL H are measured respectively2SO4With 200 mL HNO3It is placed in the round-bottomed flask that volume is 500 mL, stirs 5min
Mix.8g graphitized intermediate-phase carbospheres are weighed, are added in mixed acid, ultrasonic 20min.Then toward adding 5g in mixed liquor
CrO3, 7h is stirred at a temperature of 40 DEG C.After question response terminates, room temperature is cooled to, filtering obtains black solid.Use 5% salt
Acid solution cleans five times, is then washed repeatedly to neutrality with distilled water, and in vacuum environment, dried at a temperature of 80 DEG C.So
Dry black solid is placed in quartz tube furnace afterwards.Be passed through argon gas as protection gas, gas flow 200mL/min, with
10 DEG C/min heating rate is incubated 15min from room temperature to 950 DEG C, fast cooling is then carried out to room temperature, so as to obtain
Burning forging product.Obtained calcined product is collected, it is standby.
Embodiment 3
150mL H are measured respectively2SO4With 100 mL H3PO4It is placed in the round-bottomed flask that volume is 500 mL, stirring
10min is mixed.5g graphitized intermediate-phase carbospheres are weighed, are added in mixed acid, ultrasonic 20min.Then toward in mixed liquor plus
Enter 2g CrO3, 24h is stirred at a temperature of 60 DEG C.After question response terminates, room temperature is cooled to, filtering obtains black solid.Use
10% hydrochloric acid solution cleans five times, is then washed repeatedly to neutrality with distilled water, and in vacuum environment, at a temperature of 80 DEG C
Drying.Then dry black solid is placed in quartz tube furnace.Helium is passed through as protection gas, gas flow 150mL/
Min, with 15 DEG C/min heating rate from room temperature to 1000 DEG C, 10min is incubated, then progress fast cooling to room temperature,
So as to obtain burning forging product.Obtained calcined product is collected, it is standby.
Embodiment 4
200mL H are measured respectively2SO4With 80 mL HClO4It is placed in the round-bottomed flask that volume is 500 mL, stirs 20min
Mix.10g graphitized intermediate-phase carbospheres are weighed, are added in mixed acid, ultrasonic 10min.Then toward adding 4g in mixed liquor
CrO3, 12h is stirred at a temperature of 25 DEG C.After question response terminates, room temperature is cooled to, filtering obtains black solid.Use 8%
Hydrochloric acid solution cleans five times, is then washed repeatedly to neutrality with distilled water, and in vacuum environment, dried at a temperature of 80 DEG C.
Then dry black solid is placed in quartz tube furnace.The mixed gas of argon gas and nitrogen is passed through as protection gas, gas
Flow is 150mL/min, with 10 DEG C/min heating rate from room temperature to 950 DEG C, is incubated 10min, is then carried out quick
Room temperature is cooled to, so as to obtain burning forging product.Obtained calcined product is collected, it is standby.
Embodiment 5
150mL H are measured respectively2SO4、100mL H3PO4、80 mL HNO3It is placed in the round-bottomed flask that volume is 500 mL,
10min is stirred to mix.15g graphitized intermediate-phase carbospheres are weighed, are added in mixed acid, ultrasonic 30min.Then toward mixed liquor
Middle addition 8g CrO3, 24h is stirred at a temperature of 80 DEG C.After question response terminates, room temperature is cooled to, filtering obtains black solid.
Cleaned five times using 10% hydrochloric acid solution, then washed repeatedly to neutrality with distilled water, and in vacuum environment, 80 DEG C of temperature
Degree is lower to dry.Then dry black solid is placed in quartz tube furnace.Be passed through nitrogen is as protection gas, gas flow
200mL/min, with 20 DEG C/min heating rate from room temperature to 1050 DEG C, 10min is incubated, then carries out fast cooling extremely
Room temperature, so as to obtain burning forging product.Obtained calcined product is collected, it is standby.
Claims (7)
- A kind of 1. preparation method of the graphitized intermediate-phase carbosphere negative material of surface controllable oxidization, it is characterised in that：Including Following steps：1）Measure sulfuric acid and nitric acid, the one or more mixing of perchloric acid, phosphoric acid of certain volume, ultrasound or stirring it is certain when Between；2）A certain amount of graphitized intermediate-phase carbosphere is added in nitration mixture, ultrasound or mechanical agitation regular hour；3）A certain amount of chromium trioxide is added in above-mentioned mixed liquor, the regular hour is aoxidized under ultrasound or stirring condition, After question response terminates, room temperature is cooled to, filtering obtains black solid；4）After solid filtering, certain density hydrochloric acid and distilled water washes clean repeatedly, drying are used；5）The solid of drying is placed in tube furnace the high-temperature heat treatment regular hour under protective atmosphere and is quickly cooled to room Temperature.
- 2. preparation method according to claim 1, it is characterised in that：In step 1）, sulfuric acid dosage is 50 ~ 200mL, nitric acid Dosage is 20 ~ 200mL, perchloric acid is 20 ~ 200mL, phosphoric acid is 20 ~ 200mL, and nitration mixture is sulfuric acid and nitric acid, perchloric acid, phosphoric acid One or more mixing, ultrasonic time are 10 ~ 120min, and ultrasonic power 40-300W, ultrasonic temperature is 20 ~ 100 DEG C, or is adopted When being mixed with agitating mode, mixing time is 10 ~ 120min, and stir speed (S.S.) is 100 ~ 2000r/min.
- 3. preparation method according to claim 1, it is characterised in that：In step 2）, the use of graphitized intermediate-phase carbosphere It is 10 ~ 120min to measure as 1 ~ 20g, ultrasonic time, and ultrasonic power 40-300W, ultrasonic temperature is 20 ~ 100 DEG C, or using stirring When mode mixes, mixing time is 10 ~ 120min, and stir speed (S.S.) is 100 ~ 2000r/min.
- 4. preparation method according to claim 1, it is characterised in that：In step 3）, the dosage of chromium trioxide is 1 ~ 50g, For the temperature control of oxidation at 20 ~ 100 DEG C, the time of oxidation is 1 ~ 48h.
- 5. preparation method according to claim 1, it is characterised in that：In step 4）, the concentration of hydrochloric acid solution is 1 ~ 20%.
- 6. preparation method according to claim 1, it is characterised in that：In step 5）, the protective atmosphere of the heat treatment is Argon gas, nitrogen, helium, one kind or its person's mixed gas of hydrogen, gas flow is 50~300mL/min, with 1~20 DEG C/min Heating rate from room temperature to 600~1200 DEG C, soaking time is 10 ~ 120min, fast cooling to room temperature.
- 7. preparation method according to claim 1, it is characterised in that：In step 5）, the heat treatment mode includes microwave Heating or arc process heating.
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Effective date of registration: 20200622 Address after: 535000, the Guangxi Zhuang Autonomous Region Qinzhou District, Qinbei Real Madrid Industrial Park, a district Patentee after: GUANGXI ZHUONENG NEW ENERGY SCIENCE & TECHNOLOGY Co.,Ltd. Address before: 541004 No. 15 Yucai Road, Qixing District, Guilin, the Guangxi Zhuang Autonomous Region Patentee before: Guangxi Normal University |