CN107799752A - A kind of preparation method of nano oxidized iron particle/expansion micro crystal graphite composite for lithium ion battery - Google Patents
A kind of preparation method of nano oxidized iron particle/expansion micro crystal graphite composite for lithium ion battery Download PDFInfo
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- CN107799752A CN107799752A CN201711044838.0A CN201711044838A CN107799752A CN 107799752 A CN107799752 A CN 107799752A CN 201711044838 A CN201711044838 A CN 201711044838A CN 107799752 A CN107799752 A CN 107799752A
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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
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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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- 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 nano oxidized iron particle/expansion micro crystal graphite composite for lithium ion battery, using micro crystal graphite as raw material, carries out first time chemical graft processing and high-temperature expansion, obtains and once expand micro crystal graphite；Then once to expand micro crystal graphite and ferrocene as raw material, then once to expand micro crystal graphite and ferrocene as raw material mixing and ball milling, then carry out second and expanded obtain nano oxidized iron particle/expansion micro crystal graphite composite.High-temperature expansion method, obtained composite are tightly combined twice for the combination of the invention, and nano oxidized iron particle is uniform in expansion micro crystal graphite Dispersion on surface, and lithium storage content is higher, and circulation and high rate performance are superior.
Description
Technical field
The invention belongs to technical field of material, more particularly to a kind of for the nano oxidized of lithium ion battery
The preparation method of iron particle/expansion micro crystal graphite composite.
Background technology
Lithium ion battery is due to high output voltage and energy density, good cyclical stability and environment-friendly etc. excellent
Point, most of consumer electronics product market is captured as the power resources of various electronic products, in recent years, with
Electronic product quickly update and the continuous development in electric car market, it is desirable to which lithium ion battery has lighter matter
Amount, smaller volume and higher power density.
The expanded graphite compound between graphite layers extremely cheap as a kind of cost（GIC）, due to abundant more chis
Pore structure is spent, larger specific surface area, excellent thermoelectricity conductive performance, the advantages that good chemical stability, and is considered as
Be a kind of great potential can large-scale application in the carrier material of negative electrode of lithium ion battery.
Most of preparation of current nano particle/exfoliated-graphite composite is related to solution processes, and expanded graphite is passing through
Structure can occur significantly to change after going through solution dipping-drying course, so as to have impact on the performance of its carrier characteristics, and report
Some non-solution routes preparation method, such as high-energy ball milling, dry-mixed be only capable of realizing physical bond, it is difficult to ensure nano particle
Combine closely and uniformly divide and spread with expanded graphite.
Meanwhile the current raw material for using native graphite to be prepared for raw material used in the technology of expanded graphite meterial is generally
Crystalloid flaky graphite, although crystalline flake graphite collective orientation is good, poor orientation is needed in the application of battery material,
The good graphite material of even property, micro crystal graphite particle is tiny, and aggregate poor orientation, homogenieity is good, and micro crystal graphite can replace scale
Graphite is as the raw material for preparing the more preferable expanded graphite of electrical property, although charge specific capacity is slightly lower, charge efficiency, battery are steady
Qualitative and cycle performance can greatly improve, and still, because the expansion effect of micro crystal graphite is bad, expand micro crystal graphite and nanometer
The composite electric property of particle is had a greatly reduced quality, and nano particle/expansion is prepared using expansion micro crystal graphite in prior art
Graphite composite material does not reach its due excellent electric property, how to improve expansion effect and the expansion of micro crystal graphite
The composite effect of micro crystal graphite and nano-particle material is current the problem of being badly in need of research.
The content of the invention
The purpose of the present invention is the problem of presence for prior art, there is provided a kind of for the nano oxidized of lithium ion battery
The preparation method of iron particle/expansion micro crystal graphite composite.
Another object of the present invention is to provide a kind of nano oxidized iron particle/expansion microlite for lithium ion battery
Black composite.
Further object of the present invention is to provide nano oxidized iron particle/expansion micro crystal graphite composite as lithium ion
The application of cell negative electrode material.
The purpose of the present invention is achieved by the following technical programs：
A kind of preparation method of nano oxidized iron particle/expansion micro crystal graphite composite for lithium ion battery, is with micro-
Spar ink is raw material, carries out first time chemical graft processing, then the product after intercalation processing is filtered, washed and done
It is dry, obtain and once may expand micro crystal graphite, micro crystal graphite is may expand to gained in graphite expansion stove at 800 DEG C uses high-temperature expansion
Method carries out so expanded that once to expand micro crystal graphite；Then once to expand micro crystal graphite and ferrocene as raw material, once expand micro-
Spar ink and ferrocene in mass ratio 1:2 ~ 10 ratio mixing and ball milling, then ball milling is mixed in graphite expansion stove at 900 DEG C
Conjunction material obtains nano oxidized iron particle/expansion micro crystal graphite composite using the progress of high-temperature expansion method is expanded for the second time.
The invention using micro crystal graphite be raw material, first carry out chemical graft, then using a preexpanding at
Reason, expand micro crystal graphite gap, then using the expansion micro crystal graphite after expansion and ferrocene as raw material, first carry out mixing ball
Mill, reexpansion processing is then carried out, in second of expansion procedure, expansion micro crystal graphite is expanded again, increases crystallite
The expansion multiple of graphite, expanded while, ferrocene distillation is decomposed, and gas phase permeates into expanded graphite table in expanded space
Face, nano oxidized iron particle is realized in the dispersed of expansion micro crystal graphite surface, and be tightly combined with expanded graphite, disperse
Uniformly.
Preferably, the micro crystal graphite is Chenzhou City Shandong pool graphite powder, and its carbon content is 70 ~ 80%.
The preparation method of nano oxidized iron particle/expansion micro crystal graphite composite in the present invention, including graphite expansion stove,
Using high-temperature expansion method, following steps are specifically included：
S1. micro crystal graphite raw material, crushing and grinding, to the microlite ink powder that granularity is 300 ~ 400 mesh are taken；
S2. the potassium permanganate pure with the perchloric acid and chemistry of mass fraction 70% of microlite ink powder obtained by step S1 is placed in reaction
First time chemical graft processing is carried out in device, inflatable micro crystal graphite acidic suspension is obtained, microlite may expand to gained
Black acidic suspension filtering, reservation filtrate is standby, then washs filtrate, dries, obtains and once may expand micro crystal graphite；
S3. micro crystal graphite will be once may expand obtained by step S2 to be placed in graphite expansion stove, and first time high temperature is carried out at 800 DEG C
Expansion, is once expanded micro crystal graphite；
S4. micro crystal graphite and ferrocene in mass ratio 1 will be once expanded obtained by step S3:2 ~ 10 ratio mixing is placed in ball mill
Middle ball milling mixing；
S5. the compound after ball milling obtained by step S4 is placed in graphite expansion stove, it is swollen that second of high temperature is carried out at 900 DEG C
It is swollen, obtain nano oxidized iron particle/expansion micro crystal graphite composite.
It is 30 μm that filter membrane maximum diameter of hole used is filtered described in step S2；The washing refers to crossing 10% hydrochloric acid of filter residue
Washing 3 ~ 5 times, then be washed with deionized to 7 or so；The drying refers to dries 2h under the conditions of 60 ~ 80 DEG C.
Preferably, first time chemical graft step includes described in step S2：
S21. it is 10~30 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；
S22. it is 1 by the mass ratio of the micro crystal graphite powder and potassium permanganate：2~8 add potassium permanganate, are stirred at room temperature
After uniformly, it is warming up to 30~60 DEG C and continues 1~3.0h of stirring reaction；
S23. add deionized water the temperature in the reaction unit is increased to 60~100 DEG C, be further continued for stirring reaction 1~
3.0h。
Preferably, step S3 carries out first time high-temperature expansion in graphite expansion stove and comprised the following steps：
S31. feed：Using conserving graphite expanding furnace, an expansible graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；
S32. expand：The expansion temperature of burner hearth is 800 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S33. discharge：After completing step S32, discharging opening temperature is 50 DEG C, is then collected in discharge outlet and is once expanded stone
Ink.
Preferably, ratio of grinding media to material is 3 ~ 5 in step S4:1, Ball-milling Time is 8 ~ 10h.
Preferably, step S5 carries out second of high-temperature expansion in graphite expansion stove and comprised the following steps：
S51. feed：Using conserving graphite expanding furnace, ball milling mixing material is put into burner hearth by charging aperture, the temperature of the charging aperture
Spend for 30 DEG C, dispensing speed is 2Kg/h；
S52. expand：The expansion temperature of burner hearth is 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S53. discharge：After completing step S52, discharging opening temperature is 50 DEG C, then collects to obtain nano-sized iron oxide in discharge outlet
Particle/expansion micro crystal graphite composite.
Preparation method of the present invention including nano oxidized iron particle/expansion micro crystal graphite composite obtains nano oxidized
Iron particle/expansion micro crystal graphite composite.
Nano oxidized iron particle/expansion micro crystal graphite composite is used as the negative pole of lithium ion battery in the present invention.
Compared with the prior art, the beneficial effects of the present invention are：
（1）The present invention prepares expansion microcrystalline graphite material using micro crystal graphite, is then further used as preparing nano-sized iron oxide
A kind of raw material of grain/expansion micro crystal graphite composite, there is provided new application of micro crystal graphite.
（2）The present invention uses micro crystal graphite and ferrocene to prepare nano oxidized iron particle/expansion micro crystal graphite for raw material and answered
Creative combination high-temperature expansion method twice during condensation material, first time high-temperature expansion, expands micro crystal graphite gap, then
Using the expansion micro crystal graphite after expansion and ferrocene as raw material, mixing and ball milling is first carried out, then carries out reexpansion processing,
In second of expansion procedure, expansion micro crystal graphite is expanded again, increases the expansion multiple of micro crystal graphite, expanded same
When, ferrocene distillation is decomposed, and gas phase permeates into expanded graphite surface in expanded space, realizes that nano oxidized iron particle is expanding
Micro crystal graphite surface it is dispersed, and be tightly combined, be uniformly dispersed with expanded graphite.
（3）The present invention is added without sulfur-bearing during preparing nano oxidized iron particle/expansion micro crystal graphite composite
Material, therefore in high temperature preparation process, does not produce sulfur dioxide pollution thing, the expanded graphite product of preparation yet not sulfur-bearing, system
Standby nano oxidized iron particle/expansion micro crystal graphite composite also not sulfur-bearing, improve the corrosion resistance of composite.
（4）High-temperature expansion method of the present invention, traditional high-temperature expansion method and graphite expansion stove are combined, using most
Good expansion temperature, and the stabilization of product can be effectively improved by the control to raw material and technological parameter around expansion temperature
Property.
（5）Raw material used in the method for the present invention is cheap, with short production cycle, have obvious social and economic benefits,
It is easily achieved industrialized production.
（6）Composite lithium storage content produced by the present invention is higher, and circulation and high rate performance are superior.
Brief description of the drawings
Fig. 1 is the high temperature graphite expansion furnace structure figure of embodiment 1 ~ 5.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Following examples are only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
Embodiment 1
The method that the present invention prepares expansion microcrystalline graphite material with micro crystal graphite, including step are as follows：Including graphite expansion stove, adopt
With high-temperature expansion method, comprise the following steps：
S1. micro crystal graphite raw material, phosphorus content 70%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh are taken；
S2. microlite ink powder obtained by step S1 is placed in reaction unit with perchloric acid and potassium permanganate and carries out chemical for the first time insert
Layer processing, inflatable micro crystal graphite acidic suspension is obtained, the filtering of micro crystal graphite acidic suspension is may expand to gained, retains filter
Liquid is standby, then washs filtrate, dries, obtains and once may expand micro crystal graphite；Wherein, the tool of first time chemical graft
Body step is：S21. it is 10 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S22. crystallite is pressed
The mass ratio of graphite composite powder and strong oxidizer is 2：1 adds strong oxidizer, after being stirred at room temperature uniformly, is warming up to 30 DEG C of continuation
Stirring reaction 3h；S23. adding deionized water makes the temperature in reaction unit be increased to 60 DEG C, is further continued for stirring reaction 3h；
S3. micro crystal graphite will be once may expand obtained by step S2 to be placed in graphite expansion stove, is carried out first time high-temperature expansion, is obtained
Once expand micro crystal graphite；Wherein first time high-temperature expansion concretely comprises the following steps：S31. feed：, can using conserving graphite expanding furnace
Expanded graphite is put into burner hearth by charging aperture, and the temperature of the charging aperture is 30 DEG C, and dispensing speed is 2Kg/h；S32. it is swollen
It is swollen：The expansion temperature of burner hearth is 800 DEG C, by controlled wind speed come to control Bulking Time be 5s；S33. discharge：Complete step S52
Afterwards, discharging opening temperature is 50 DEG C, then collects to obtain an expanded graphite in discharge outlet；
S4. by an expanded graphite obtained by step S3 and ferrocene in mass ratio 1:5, ratio of grinding media to material 4:1 ratio mixing is placed in
Ball milling 8h in ball mill；
S5. the compound after ball milling obtained by step S4 is placed in graphite expansion stove, it is swollen that second of high temperature is carried out at 900 DEG C
It is swollen, obtain nano oxidized iron particle/expansion micro crystal graphite composite；Wherein second high-temperature expansion concretely comprises the following steps：
S51. feed：Using conserving graphite expanding furnace, expansible graphite is put into burner hearth by charging aperture, the temperature of the charging aperture is
30 DEG C, dispensing speed is 2Kg/h；S52. expand：The expansion temperature of burner hearth is 900 DEG C, during by controlled wind speed to control expansion
Between be 5s；S53. discharge：After completing step S52, discharging opening temperature is 50 DEG C, then collects to obtain in discharge outlet nano oxidized
Iron particle/expansion micro crystal graphite composite.
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 150, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 200m2/g。
Nano oxidized iron particle/expansion micro crystal graphite composite is under 50mA/g current density obtained by the present embodiment
First charge-discharge capacity still possesses 639mAh/g reversible capacity up to 650mAh/g after 50 circulations.
Embodiment 2
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material, phosphorus content 70%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh are taken；
S2. first time chemical graft concretely comprises the following steps：S21. it is 15 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/
Kg is mixed evenly；S22. it is 4 by the mass ratio of micro crystal graphite powder and potassium permanganate：1 adds potassium permanganate, at room temperature
After stirring, it is warming up to 40 DEG C and continues stirring reaction 2h；S23. adding deionized water is increased to the temperature in reaction unit
70 DEG C, it is further continued for stirring reaction 2h；
S4. by an expanded graphite obtained by step S3 and ferrocene in mass ratio 1:2, ratio of grinding media to material 3:1 ratio mixing is placed in
Ball milling 10h in ball mill；
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 180, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area 302m2/g。
Nano oxidized iron particle/expansion micro crystal graphite composite is under 50mA/g current density obtained by the present embodiment
First charge-discharge capacity still possesses 625mAh/g reversible capacity up to 638mAh/g after 50 circulations.
Embodiment 3
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material, phosphorus content 75%, crushing and grinding, to the microlite ink powder that granularity is 350 mesh are taken；
S2. first time chemical graft concretely comprises the following steps：S21. it is 20 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/
Kg is mixed evenly；S22. it is 6 by the mass ratio of micro crystal graphite powder and potassium permanganate：1 adds potassium permanganate, at room temperature
After stirring, it is warming up to 50 DEG C and continues stirring reaction 2h；S23. adding deionized water is increased to the temperature in reaction unit
80 DEG C, it is further continued for stirring reaction 2h；
S4. by an expanded graphite obtained by step S3 and ferrocene in mass ratio 1:3, ratio of grinding media to material 3:1 ratio mixing is placed in
Ball milling 10h in ball mill；
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 160, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area 410m2/g。
Nano oxidized iron particle/expansion micro crystal graphite composite is under 50mA/g current density obtained by the present embodiment
First charge-discharge capacity still possesses 624mAh/g reversible capacity up to 640mAh/g after 50 circulations.
Embodiment 4
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material, phosphorus content 75%, crushing and grinding, to the microlite ink powder that granularity is 350 mesh are taken；
S2. first time chemical graft concretely comprises the following steps：S21. it is 20 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/
Kg is mixed evenly；S22. it is 6 by the mass ratio of micro crystal graphite powder and potassium permanganate：1 adds potassium permanganate, at room temperature
After stirring, it is warming up to 50 DEG C and continues stirring reaction 1h；S23. adding deionized water is increased to the temperature in reaction unit
90 DEG C, it is further continued for stirring reaction 1h；
S4. by an expanded graphite obtained by step S3 and ferrocene in mass ratio 1:8, ratio of grinding media to material 5:1 ratio mixing is placed in
Ball milling 8h in ball mill；；
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 198, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area 393m2/g。
Nano oxidized iron particle/expansion micro crystal graphite composite is under 50mA/g current density obtained by the present embodiment
First charge-discharge capacity still possesses 644mAh/g reversible capacity up to 653mAh/g after 50 circulations.
Embodiment 5
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material, phosphorus content 80%, crushing and grinding, to the microlite ink powder that granularity is 350 mesh are taken；
S2. first time chemical graft concretely comprises the following steps：S21. it is 25 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/
Kg is mixed evenly；S22. it is 7 by the mass ratio of micro crystal graphite powder and potassium permanganate：1 adds potassium permanganate, at room temperature
After stirring, it is warming up to 60 DEG C and continues stirring reaction 1h；S23. adding deionized water is increased to the temperature in reaction unit
100 DEG C, it is further continued for stirring reaction 1h；
S4. by an expanded graphite obtained by step S3 and ferrocene in mass ratio 1:10, ratio of grinding media to material 5:1 ratio mixing is placed in
Ball milling 10h in ball mill；；
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 201, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area 200m2/g。
Nano oxidized iron particle/expansion micro crystal graphite composite is under 50mA/g current density obtained by the present embodiment
First charge-discharge capacity still possesses 631mAh/g reversible capacity up to 643mAh/g after 50 circulations.
Embodiment 6
Referring to Fig. 1, the graphite expansion stove that is used for the first time high-temperature expansion of embodiment 1 to 5 and second of high-temperature expansion process,
Graphite expansion stove includes body of heater 1, feeding device 2, drawing mechanism 3 and control device, and raw material is by feeding device 2 to body of heater 1, so
Collected afterwards by drawing mechanism 3；Drawing mechanism 3 is located above body of heater, and feeding device 2 is located at below body of heater；It is provided with and adds in body of heater 1
Thermal 11, using Resistant heating, the inner bottom part of body of heater 1 is additionally provided with air-flow shower nozzle 4, and air-flow shower nozzle 4 also includes source of the gas 41, air-flow
Pipeline 42 and control damper 43, source of the gas 41 is air, and connects airflow line 42, and airflow line 42 connects air-flow shower nozzle 4, gas
Flow control valve 43 is located in airflow line 42, and the top of air-flow shower nozzle 4 is provided with feeding device 2, specifically using feed screw, control
Device includes processor 5 and controller, and processor 5 is provided with control panel and is connected with controller, and controller includes the first control
Device 53, the controller 51 of second controller 52 and the 3rd, the first controller 53 are connected with the control damper 43 of air-flow shower nozzle 4, the
Two controllers 52 are connected with feeding device 2, and the 3rd controller 51 is connected with heater 11；
Wherein, processor 5 uses microprocessor, and the first controller uses air inlet valve-driving circuit, and second controller is using charging
Valve-driving circuit, the 3rd controller use heat driven circuit.
Cooling device 7 is additionally provided between drawing mechanism 3 and body of heater 1, cooling device 7 includes heat exchanger tube 71 and water cooling tube 72,
One end connection body of heater 1 of heat exchanger tube 71, other end connection drawing mechanism 3, heat exchanger tube 71 and horizontal angle are 45 DEG C~90
DEG C, water cooling tube 72 is arranged on heat exchanger tube 71 in the shape of a spiral；
Drawing mechanism 3 includes multiple reserves storehouses 31 and connecting pipe 32, and the one end of connecting pipe 32 is connected with heat exchanger tube 71, and is provided with
Cyclone separator 33, the other end are connected with exhaust outlet 34, be additionally provided with connecting pipe 32 multiple subtubes 35 respectively with reserves storehouse
31 connections；Connecting pipe and 32 horizontal angles are 45 DEG C~90 DEG C；
Agitator 8 is additionally provided with body of heater 1, agitator 8 is spiral agitator, is coordinated by motor and ball-screw so that stir
Mix device 8 and upper and lower linear motion is done in body of heater 1, so as to drive the airflow reflux in body of heater 1.
Wherein：The temperature of discharging opening is controlled by cooling device, and heater 6 also is provided with to control in charging aperture
The temperature of charging aperture processed, specific the present embodiment can be heated using resistance wire 61 to the discharge pipe in feeding device.
Can control time and the temperature of expansion by control panel, specifically processor by control the first controller and
Second controller controls air velocity and charging rate, so as to control the reaction time that intercalated graphite expands, the 3rd controller
The temperature of heater can be controlled, the intellectuality of graphite expansion is realized, reaches and be precisely controlled.
Graphite expansion stove is placed using two floors, and the processing sequence according to raw material is heat exchanger tube and connection from the bottom up
Pipeline and horizontal line have certain angle, by the cooperation of gravity and wind speed, that is, solve expanded graphite and get stuck problem, improve anti-
Yield is answered, while also solves space compared to being disposed vertically.
Graphite expansion stove adds agitator 8 in body of heater 1 so that the air-flow in body of heater 1 forms convection current, ensure that intercalation stone
Ink is heated evenly, so as to which the expanded reaction efficiency of intercalated graphite be significantly increased..
Comparative example 1
Comparative example 1 is with the difference of embodiment 1：First time high-temperature expansion and second of high-temperature expansion are without using high-temperature expansion
Stove, using traditional Muffle furnace, coordinate high-temperature expansion method, specifically different steps is as follows：
S3. micro crystal graphite will be once may expand obtained by step S2 it is placed in Muffle furnace and heat calcination process, the is carried out at 800 DEG C
High-temperature expansion, Bulking Time 30s, is once expanded micro crystal graphite；
S5. ball milling mixing material obtained by step S4 is placed in Muffle furnace and heats calcination process, second of high temperature is carried out at 900 DEG C
Expansion, Bulking Time 30s, obtains nano oxidized iron particle/expansion micro crystal graphite composite.
The expansion multiple that micro crystal graphite is once expanded obtained by this comparative example is 122, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 296m2/g。
Nano oxidized iron particle/expansion micro crystal graphite composite is under 50mA/g current density obtained by this comparative example
First charge-discharge capacity is 593mAh/g, there is 552mAh/g reversible capacity after 50 circulations.
Claims (10)
1. a kind of preparation method of nano oxidized iron particle/expansion micro crystal graphite composite for lithium ion battery, it is special
Sign is, is using micro crystal graphite as raw material, carries out first time chemical graft processing, then the product after intercalation processing was carried out
Filter, wash and dry, obtain and once may expand micro crystal graphite, micro crystal graphite may expand to gained in graphite expansion stove at 800 DEG C
Carried out using high-temperature expansion method so expanded that once to expand micro crystal graphite；Then once to expand micro crystal graphite and ferrocene as original
Material, once expand micro crystal graphite and ferrocene in mass ratio 1:2 ~ 10 ratio mixing and ball milling, then at 900 DEG C in graphite expansion
It is expanded for the second time that nano oxidized iron particle/expansion micro crystal graphite is compound using the progress of high-temperature expansion method to ball milling mixing material in stove
Material.
2. the preparation method of nano oxidized iron particle/expansion micro crystal graphite composite, its feature exist according to claim 1
In the micro crystal graphite is Chenzhou City Shandong pool graphite powder, and its carbon content is 70 ~ 80%.
3. the preparation method of nano oxidized iron particle/expansion micro crystal graphite composite, its feature exist according to claim 1
In, including graphite expansion stove, using high-temperature expansion method, comprise the following steps：
S1. micro crystal graphite raw material, crushing and grinding, to the microlite ink powder that granularity is 300 ~ 400 mesh are taken；
S2. the potassium permanganate pure with the perchloric acid and chemistry of mass fraction 70% of microlite ink powder obtained by step S1 is placed in reaction
First time chemical graft processing is carried out in device, inflatable micro crystal graphite acidic suspension is obtained, microlite may expand to gained
Black acidic suspension filtering, reservation filtrate is standby, then washs filtrate, dries, obtains and once may expand micro crystal graphite；
S3. micro crystal graphite will be once may expand obtained by step S2 to be placed in graphite expansion stove, and first time high temperature is carried out at 800 DEG C
Expansion, is once expanded micro crystal graphite；
S4. micro crystal graphite and ferrocene in mass ratio 1 will be once expanded obtained by step S3:2 ~ 10 ratio mixing is placed in ball mill
Middle ball milling mixing；
S5. the compound after ball milling obtained by step S4 is placed in graphite expansion stove, it is swollen that second of high temperature is carried out at 900 DEG C
It is swollen, obtain nano oxidized iron particle/expansion micro crystal graphite composite.
4. the preparation method of nano oxidized iron particle/expansion micro crystal graphite composite, its feature exist according to claim 3
In it is 30 μm that filter membrane maximum diameter of hole used is filtered described in step S2；The washing refer to cross filter residue with 10% salt acid elution 3 ~
5 times, then be washed with deionized to 7 or so；The drying refers to dries 2h under the conditions of 60 ~ 80 DEG C.
5. the preparation method of nano oxidized iron particle/expansion micro crystal graphite composite, its feature exist according to claim 3
In first time described in step S2, chemical graft step included：
S21. it is 10~30 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；
S22. it is 1 by the mass ratio of the micro crystal graphite powder and potassium permanganate：2~8 add potassium permanganate, are stirred at room temperature
After uniformly, it is warming up to 30~60 DEG C and continues 1~3.0h of stirring reaction；
S23. add deionized water the temperature in the reaction unit is increased to 60~100 DEG C, be further continued for stirring reaction 1~
3.0h。
6. the preparation method of nano oxidized iron particle/expansion micro crystal graphite composite, its feature exist according to claim 3
In step S3 carries out first time high-temperature expansion in graphite expansion stove and comprised the following steps：
S31. feed：Using conserving graphite expanding furnace, an expansible graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；
S32. expand：The expansion temperature of burner hearth is 800 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S33. discharge：After completing step S32, discharging opening temperature is 50 DEG C, is then collected in discharge outlet and is once expanded stone
Ink.
7. the preparation method of nano oxidized iron particle/expansion micro crystal graphite composite, its feature exist according to claim 4
In ratio of grinding media to material is 3 ~ 5 in step S4:1, Ball-milling Time is 8 ~ 10h.
8. the preparation method of nano oxidized iron particle/expansion micro crystal graphite composite, its feature exist according to claim 3
In step S5 carries out second of high-temperature expansion in graphite expansion stove and comprised the following steps：
S51. feed：Using conserving graphite expanding furnace, ball milling mixing material is put into burner hearth by charging aperture, the temperature of the charging aperture
Spend for 30 DEG C, dispensing speed is 2Kg/h；
S52. expand：The expansion temperature of burner hearth is 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S53. discharge：After completing step S52, discharging opening temperature is 50 DEG C, then collects to obtain nano-sized iron oxide in discharge outlet
Particle/expansion micro crystal graphite composite.
9. the preparation side of nano oxidized iron particle/expansion micro crystal graphite composite according to claim 1~8 any one
The nano oxidized iron particle that method obtains/expansion micro crystal graphite composite.
10. nano oxidized iron particle described in claim 9/expansion micro crystal graphite composite is used as the negative pole of lithium ion battery.
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