CN105336953A - Surface controllable oxidation graphitization mesophase carbon nanosphere negative electrode material and preparation method - Google Patents
Surface controllable oxidation graphitization mesophase carbon nanosphere negative electrode material and preparation method Download PDFInfo
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- CN105336953A CN105336953A CN201510639980.4A CN201510639980A CN105336953A CN 105336953 A CN105336953 A CN 105336953A CN 201510639980 A CN201510639980 A CN 201510639980A CN 105336953 A CN105336953 A CN 105336953A
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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 present invention discloses a surface controllable oxidation graphitization mesophase carbon nanosphere negative electrode material and a preparation method. The method comprises the following steps: 1) measuring a certain volume of sulfuric acid to mix with one or more than one of nitric acid, perchloric acid and phosphoric acid, and ultrasonically processing or stirring for a certain time; 2) measuring a certain amount of graphitization mesophase carbon nanospheres to add into the mixed acid, ultrasonically processing or mechanically stirring for a certain time; 3) adding a certain amount of chromium trioxide into the liquid mixture, ultrasonically processing or mechanically stirring for oxidation for a certain time, and after completion of the reaction, filtering to obtain a black solid; 4 ) after filtration, using repeatedly washing with a certain concentration of hydrochloric acid and distilled water to clean, and drying; and 5) putting the dried solid into a tube furnace for high temperature heat treatment for some time a certain time in a protective atmosphere and cooling to room temperature. The surface controllable oxidation graphitization mesophase carbon nanosphere has lower lithium-intercalation removal platform and high platform capacity, and has a good degree of graphitization and excellent cycle performance.
Description
Technical field
The present invention relates to a kind of lithium cell cathode material and preparation method thereof, graphitized intermediate-phase carbosphere negative material particularly relating to a kind of surperficial controllable oxidization and preparation method thereof.
Background technology
Lithium ion battery, as the important component part of electronic product, makes it in the life of people, play more and more important role.In recent years, due to electric automobile and hybrid-electric car fast development, people were made urgently to wish the battery of the power-type lithium ion developing height ratio capacity and high-energy-density.The research of lithium ion battery negative material is most important for the research and development of the battery of power-type lithium ion.First high-performance negative material must meet two large basic demands: (1) has lower oxidation-reduction potential platform, makes battery have higher output voltage; (2) embed and deviate from lithium ion as much as possible, making battery have high specific capacity and energy density.Current, business-like ion cathode material lithium is mainly based on graphite type material.Graphite has special layer structure, and connect with more weak Van der Waals force between phase interconnect layer, interlamellar spacing is 0.3354nm.This favourable structure makes lithium ion can embed the interlayer of graphite and not destroy its structure, forms compound between graphite layers.Lithium ion (0.01 ~ 0.25V) can be embedded into graphite layers under lower electromotive force, and to be somebody's turn to do " low embedding lithium electromotive force " be the basic premise guaranteeing battery " high output voltage ".But the theoretical specific capacity of graphite cathode material is only 372mAh/g, the requirement of high-performance negative material not yet can be reached.
In numerous graphite material, graphitized intermediate-phase carbon microballoon (GMCMB) gets the attention and highly approves.Compared with Conventional graphite material, GMCMB also has two large advantages: (1) spherical structure can realize the tightly packed of material, can prepare high-density electrode; (2) spherome surface is smooth, and specific area is low, decreases the generation of side reaction, improves first charge-discharge efficiency.Above-mentioned advantage makes GMCMB become a kind of negative material having application prospect.However, GMCMB is still faced with the not high enough bottleneck problem of specific capacity in actual applications.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, a kind of method of effective GMCMB modification is " oxidationreduction " process, and namely by chemical oxidation, carry out surface oxidation modification to GMCMB, object improves the chemical property of GMCMB.GMCMB is placed in ammonia atmosphere by the people such as such as Han, and reaction temperature is 800 DEG C, has successfully prepared nitrating GMCMB.
Although oxidation processes can be modified GMCMB, easily there is the phenomenon of over oxidation.Due to over oxidation, the spherical structure of carbonaceous mesophase spherules is destroyed, bulk density reduce, degree of graphitization reduce, as during negative pole conductivity reduce, cycle performance decline.
The present invention carries out finishing by controllable oxidization system to GMCMB, while being intended to keep GMCMB spherical structure and degree of crystallinity, improves its specific capacity and cycle performance.Adopt multiple means of testing to analyze modified GMCMB negative material, inquire into the correlation of method of modifying and pattern, structure and chemical property.
Summary of the invention
The object of the invention is the specific capacity in order to improve graphitized intermediate-phase carbosphere and cyclical stability, graphitized intermediate-phase carbosphere negative material providing a kind of surperficial controllable oxidization and preparation method thereof.The main process of the method carries out ultrasonic to the mixed liquor of graphitized intermediate-phase carbosphere and sulfuric acid, nitric acid, phosphoric acid etc., then adopt chromium trioxide to be oxidized graphitized intermediate-phase carbosphere, make graphitized intermediate-phase carbosphere that good spherical structure can be kept to improve surface topography again.Surface controllable oxidization keeps the spherical structure of graphitized intermediate-phase carbosphere on the one hand, guarantees the bulk density of material, can increase the storage lithium site on graphitized intermediate-phase carbosphere surface on the other hand, improves the specific capacity of material.Controllable oxidization graphitized intermediate-phase carbosphere (EMCMB) can keep the spherical structure of carbosphere, good degree of graphitization, can increase again specific capacity and the cycle performance of carbosphere.
The graphitized intermediate-phase carbosphere lithium cell cathode material of surperficial controllable oxidization of the present invention, has good spherical structure, carries out controlled oxidation to its surface, carries out the modification of appropriateness.The present invention also provides the preparation method of the graphitized intermediate-phase carbosphere lithium cell cathode material of above-mentioned surperficial controllable oxidization.The method comprises the steps:
1) one or more mixing of the sulfuric acid of certain volume and nitric acid, perchloric acid, phosphoric acid are measured, ultrasonic or stir the regular hour;
2) a certain amount of graphitized intermediate-phase carbosphere is joined in nitration mixture, the ultrasonic or mechanical agitation regular hour;
3) a certain amount of chromium trioxide is joined in above-mentioned mixed liquor, under ultrasonic or stirring condition, be oxidized the regular hour, after question response terminates, be cooled to room temperature, filter and obtain black solid;
4), after solid filtering, use certain density hydrochloric acid and distilled water cyclic washing totally, dry;
5) solid of oven dry is placed in tube furnace high-temperature heat treatment regular hour be quickly cooled to room temperature under protective atmosphere.
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, nitration mixture be sulfuric acid with nitric acid, perchloric acid, phosphoric acid one or more mix, ultrasonic time is 10 ~ 120min, ultrasonic power is 40-300W, and ultrasonic temperature is 20 ~ 100
oc, or when adopting agitating mode to mix, mixing time is 10 ~ 120min, and stir speed (S.S.) is 100 ~ 2000r/min.
In step 2) in, the consumption of graphitized intermediate-phase carbosphere is 1 ~ 20g, and ultrasonic time is 10 ~ 120min, and ultrasonic power is 40-300W, and ultrasonic temperature is 20 ~ 100
oc, or when adopting agitating mode to mix, mixing time is 10 ~ 120min, and stir speed (S.S.) is 100 ~ 2000r/min.
In step 3), the consumption of chromium oxide is 1 ~ 50g, and the temperature of oxidation controls 20 ~ 100
oc, the time of oxidation is 1 ~ 48h.
In step 4), the concentration of hydrochloric acid solution is 1 ~ 20%.
In step 5), described heat treated protective atmosphere is argon gas, nitrogen, helium, the one of hydrogen or its person's mist, and gas flow is 50 ~ 300mL/min, with 1 ~ 20
oCthe heating rate of/min is from room temperature to 600 ~ 1200
oC, temperature retention time is 10 ~ 120min, and fast cooling is to room temperature.Described heat treatment mode comprises microwave heating, arc process heating.
Advantage of the present invention: the graphitized intermediate-phase carbosphere carbon-coating of surperficial controllable oxidization is strutted by appropriateness, and surface has lamellar structure, can promote the immersion of electrolyte and the transmission of ion.Surface controllable oxidization carries out the oxidation processes on surface to graphitized intermediate-phase carbosphere, avoid the spherical destruction that over oxidation causes graphitized intermediate-phase carbosphere, and degree of crystallinity declines, the problems such as internal resistance increase.Keep the spherical structure of graphitized intermediate-phase carbosphere on the one hand, guarantee the bulk density of material, the storage lithium site on graphitized intermediate-phase carbosphere surface can be increased on the other hand, improve the specific capacity of material.The graphitized intermediate-phase carbosphere of surface controllable oxidization has lower removal lithium embedded platform, higher platform capacity.Meanwhile, there is good degree of graphitization and the cycle performance of excellence.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the graphitized intermediate-phase carbosphere of controllable oxidization of the present invention;
Fig. 2 is the XRD of the graphitized intermediate-phase carbosphere of the graphitized intermediate-phase carbosphere raw material that uses of the present invention and controllable oxidization;
Fig. 3 is the charging and discharging curve figure of the graphitized intermediate-phase carbosphere of the graphitized intermediate-phase carbosphere raw material that uses of the present invention and controllable oxidization;
Fig. 4 is the cycle performance figure of the graphitized intermediate-phase carbosphere of the graphitized intermediate-phase carbosphere raw material that uses of the present invention and controllable oxidization;
Fig. 5 is the high rate performance figure of the graphitized intermediate-phase carbosphere of the graphitized intermediate-phase carbosphere raw material that uses of the present invention and controllable oxidization.
Embodiment
Embodiment 1
Measure 150mLH respectively
2sO
4and 180mLHNO
3be placed in the round-bottomed flask that volume is 500mL, stir 5min mixing.Take 8g graphitized intermediate-phase carbosphere, join in mixed acid, ultrasonic 20min.Then in mixed liquor, 3gCrO is added
3, 40
oCtemperature under stir 7h.After question response terminates, be cooled to room temperature, filter and obtain black solid.Use the hydrochloric acid solution of 5% to clean five times, then use distilled water cyclic washing to neutral, and in vacuum environment, 80
oCtemperature under dry.Then the black solid of drying is placed in quartz tube furnace.Pass into argon gas as protection gas, gas flow is 100mL/min, with 10
othe heating rate of C/min is from room temperature to 800
oc, insulation 10min, then carries out fast cooling to room temperature, thus obtains burning forging product.Collect the calcined product obtained, for subsequent use.
The pattern of graphitization mesocarbon microbeads prepared by controllable oxidization as shown in Figure 1.The Electronic Speculum figure of the graphitization mesocarbon microbeads that Fig. 1 (a) is controllable oxidization under low range, as can be seen from the figure, after controllable oxidization, carbonaceous mesophase spherules still remains spherical structure.The Electronic Speculum figure of the graphitization mesocarbon microbeads that Fig. 1 (b) is controllable oxidization under high magnification, obviously find out from figure, graphitized intermediate-phase carbosphere obtains the oxidation of appropriateness, and it keeps spherical structure, graphite linings is slightly strutted, and the structure of some cracks and lamella appears in surface.
As can be seen from the data of the XRD of Fig. 2, graphitization mesocarbon microbeads prepared by controllable oxidization remains good degree of crystallinity.
With the graphitization mesocarbon microbeads of obtained controllable oxidization, binding agent (PVDF), the mass ratio of conductive carbon black (SP) is that 80:10:10 is coated on as negative pole in Copper Foil, using metal lithium sheet as to electrode, is assembled into button cell.It is in the ethylene carbonate of 1:1 and the mixed solvent of propene carbonate that the electrolyte consisting of 1 mole of hexafluoro phosphorus lithium of electrolyte is dissolved in volume ratio.Button cell is tested under the current density of 100mA/g.
As seen from Figure 3, except discharge curve first, the graphitization mesocarbon microbeads of controllable oxidization is the same with used graphitized intermediate-phase carbosphere, has lower embedding lithium platform.The discharge and recharge data of associative list 1 can be found out, the graphitization mesocarbon microbeads of controllable oxidization is compared with used graphitized intermediate-phase carbosphere, there is higher specific capacity, the graphitized intermediate-phase carbosphere of coulombic efficiency also with used is close, illustrates that surperficial controllable oxidization can improve the specific capacity of graphitization mesocarbon microbeads.
First, second and the 5th discharge and recharge tables of data of the graphitized intermediate-phase carbosphere of the graphitized intermediate-phase carbosphere raw material that table 1 uses for the present invention and controllable oxidization.
As can be seen from Figure 4, the graphited mesocarbon microbeads of controllable oxidization is higher than the specific capacity of the graphitized intermediate-phase carbosphere used, when the graphited mesocarbon microbeads of controllable oxidization is as negative material, have good cycle performance, after 50 circulations, the specific capacity of the graphited mesocarbon microbeads of controllable oxidization still reaches 661mAh/g.
As can be seen from Figure 5, the specific capacity of the graphitization mesocarbon microbeads of controllable oxidization under different multiplying powers is all than the height of used graphitized intermediate-phase carbosphere.After different circulation, the graphitization mesocarbon microbeads of controllable oxidization, under the current density of 100mA/g, specific capacity reaches 646mAh/g, shows excellent invertibity.
Embodiment 2
Measure 130mLH respectively
2sO
4and 200mLHNO
3be placed in the round-bottomed flask that volume is 500mL, ultrasonic 5min mixing.Take 8g graphitized intermediate-phase carbosphere, join in mixed acid, stir 20min.Then in mixed liquor, 5gCrO is added
3, 40
oCtemperature under stir 7h.After question response terminates, be cooled to room temperature, filter and obtain black solid.Use the hydrochloric acid solution of 5% to clean five times, then use distilled water cyclic washing to neutral, and in vacuum environment, 80
oCtemperature under dry.Then the black solid of drying is placed in quartz tube furnace.Pass into argon gas as protection gas, gas flow is 200mL/min, with 10
othe heating rate of C/min is from room temperature to 950
oc, insulation 15min, then carries out fast cooling to room temperature, thus obtains burning forging product.Collect the calcined product obtained, for subsequent use.
Embodiment 3
Measure 150mLH respectively
2sO
4and 100mLH
3pO
4be placed in the round-bottomed flask that volume is 500mL, stir 10min mixing.Take 5g graphitized intermediate-phase carbosphere, join in mixed acid, ultrasonic 20min.Then in mixed liquor, 2gCrO is added
3, 60
oCtemperature under stir 24h.After question response terminates, be cooled to room temperature, filter and obtain black solid.Use the hydrochloric acid solution of 10% to clean five times, then use distilled water cyclic washing to neutral, and in vacuum environment, 80
oCtemperature under dry.Then the black solid of drying is placed in quartz tube furnace.Pass into helium as protection gas, gas flow is 150mL/min, with 15
othe heating rate of C/min is from room temperature to 1000
oc, insulation 10min, then carries out fast cooling to room temperature, thus obtains burning forging product.Collect the calcined product obtained, for subsequent use.
Embodiment 4
Measure 200mLH respectively
2sO
4and 80mLHClO
4be placed in the round-bottomed flask that volume is 500mL, stir 20min mixing.Take 10g graphitized intermediate-phase carbosphere, join in mixed acid, ultrasonic 10min.Then in mixed liquor, 4gCrO is added
3, 25
oCtemperature under stir 12h.After question response terminates, be cooled to room temperature, filter and obtain black solid.Use the hydrochloric acid solution of 8% to clean five times, then use distilled water cyclic washing to neutral, and in vacuum environment, 80
odry at the temperature of C.Then the black solid of drying is placed in quartz tube furnace.Pass into the mist of argon gas and nitrogen as protection gas, gas flow is 150mL/min, with 10
othe heating rate of C/min is from room temperature to 950
oc, insulation 10min, then carries out fast cooling to room temperature, thus obtains burning forging product.Collect the calcined product obtained, for subsequent use.
Embodiment 5
Measure 150mLH respectively
2sO
4, 100mLH
3pO
4, 80mLHNO
3be placed in the round-bottomed flask that volume is 500mL, stir 10min mixing.Take 15g graphitized intermediate-phase carbosphere, join in mixed acid, ultrasonic 30min.Then in mixed liquor, 8gCrO is added
3, 80
oCtemperature under stir 24h.After question response terminates, be cooled to room temperature, filter and obtain black solid.Use the hydrochloric acid solution of 10% to clean five times, then use distilled water cyclic washing to neutral, and in vacuum environment, 80
odry at the temperature of C.Then the black solid of drying is placed in quartz tube furnace.Pass into nitrogen as protection gas, gas flow is 200mL/min, with 20
othe heating rate of C/min is from room temperature to 1050
oc, insulation 10min, then carries out fast cooling to room temperature, thus obtains burning forging product.Collect the calcined product obtained, for subsequent use.
Claims (8)
1. a graphitized intermediate-phase carbosphere negative material for surperficial controllable oxidization, it is characterized in that: described graphitized intermediate-phase carbosphere has good spherical structure, and carbon-coating is strutted by appropriateness, and graphitized intermediate-phase carbosphere surface has lamellar structure.
2. a preparation method for the graphitized intermediate-phase carbosphere negative material of surperficial controllable oxidization as claimed in claim 1, is characterized in that: comprise the steps:
1) one or more mixing of the sulfuric acid of certain volume and nitric acid, perchloric acid, phosphoric acid are measured, ultrasonic or stir the regular hour;
2) a certain amount of graphitized intermediate-phase carbosphere is joined in nitration mixture, the ultrasonic or mechanical agitation regular hour;
3) a certain amount of chromium trioxide is joined in above-mentioned mixed liquor, under ultrasonic or stirring condition, be oxidized the regular hour, after question response terminates, be cooled to room temperature, filter and obtain black solid;
4), after solid filtering, use certain density hydrochloric acid and distilled water cyclic washing totally, dry;
5) solid of oven dry is placed in tube furnace high-temperature heat treatment regular hour be quickly cooled to room temperature under protective atmosphere.
3. preparation method according to claim 2, it is characterized 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, nitration mixture be sulfuric acid with nitric acid, perchloric acid, phosphoric acid one or more mix, ultrasonic time is 10 ~ 120min, ultrasonic power is 40-300W, and ultrasonic temperature is 20 ~ 100
oc, or when adopting agitating mode to mix, mixing time is 10 ~ 120min, and stir speed (S.S.) is 100 ~ 2000r/min.
4. preparation method according to claim 2, is characterized in that: in step 2), the consumption of graphitized intermediate-phase carbosphere is 1 ~ 20g, and ultrasonic time is 10 ~ 120min, and ultrasonic power is 40-300W, and ultrasonic temperature is 20 ~ 100
oc, or when adopting agitating mode to mix, mixing time is 10 ~ 120min, and stir speed (S.S.) is 100 ~ 2000r/min.
5. preparation method according to claim 2, is characterized in that: in step 3), and the consumption of chromium oxide is 1 ~ 50g, and the temperature of oxidation controls 20 ~ 100
oc, the time of oxidation is 1 ~ 48h.
6. preparation method according to claim 2, is characterized in that: in step 4), and the concentration of hydrochloric acid solution is 1 ~ 20%.
7. preparation method according to claim 2, is characterized in that: in step 5), and described heat treated protective atmosphere is argon gas, nitrogen, helium, the one of hydrogen or its person's mist, and gas flow is 50 ~ 300mL/min, with 1 ~ 20
oCthe heating rate of/min is from room temperature to 600 ~ 1200
oC, temperature retention time is 10 ~ 120min, and fast cooling is to room temperature.
8. preparation method according to claim 2, is characterized in that: in step 5), and described heat treatment mode comprises microwave heating, arc process heating.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809385A (en) * | 2019-01-25 | 2019-05-28 | 安徽益佳通电池有限公司 | A kind of lithium ion battery negative material of height ratio capacity and preparation method thereof |
| CN115367799A (en) * | 2022-09-14 | 2022-11-22 | 贵州梅岭电源有限公司 | Method for preparing high-performance chromium oxide cathode material by microwave method |
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| CN109809385A (en) * | 2019-01-25 | 2019-05-28 | 安徽益佳通电池有限公司 | A kind of lithium ion battery negative material of height ratio capacity and preparation method thereof |
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| CN115367799B (en) * | 2022-09-14 | 2023-10-31 | 贵州梅岭电源有限公司 | Method for preparing high-performance chromium oxide positive electrode material by microwave method |
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