CN109888262A - A kind of double-coating graphite composite material and its preparation method and application - Google Patents
A kind of double-coating graphite composite material and its preparation method and application Download PDFInfo
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- CN109888262A CN109888262A CN201910296809.6A CN201910296809A CN109888262A CN 109888262 A CN109888262 A CN 109888262A CN 201910296809 A CN201910296809 A CN 201910296809A CN 109888262 A CN109888262 A CN 109888262A
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Abstract
The invention discloses a kind of double-coating graphite composite materials and its preparation method and application.The method comprises the steps of: that A. prepares FeOxSolid content be 2.5-20%(weight) FeOx/ alcohol dispersion liquid, B. prepare polyethylene nitrile (PAN) coated graphite material, and C. prepares graphite@PAN@FeOxMaterial, D. graphite@C@FeOxDouble-coating composite material.The graphite@C@FeOxThe application of material is used as negative electrode material in lithium ion battery.The problem of solvent molecule that graphite@C@FeOx double-coating material prepared by the present invention eliminates the lithium ion battery in battery charging can be inserted into altogether graphite layers with lithium ion, graphite-structure variation is caused largely to decay with capacity.Therefore, graphite@C@FeOx double-coating material prepared by the present invention has superior electric cyclical stability under the premise of not reducing specific capacity, and graphite@C@FeOx double-coating structural chemistry stability is good, abundant electric cyclical stability is excellent, conductivity is high, raw material supplies abundant, cheap, green non-pollution.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of carbon, the preparation of iron oxide double-coating graphite composite material
Method and its application in the battery.
Background technique
Lithium ion battery is high with specific energy, abundant electric life is long, environmental pollution is small, charging rate is fast low with self-discharge rate
The advantages that, before the fields such as portable electronic device, electronic work/toy, green traffic, extensive energy storage have a wide range of applications
Scape.From the point of view of the material of battery composition, negative electrode material is one of important component of lithium ion battery.It is sent out in lithium ion battery
In exhibition course, there is Li+The successful exploitation of the graphite negative electrodes material of insertion reaction mechanism is that lithium ion battery trend is extensive
The key and lithium ion battery of application negative electrode material product most widely used at present.Even if in the battery of some other classifications
In product, electric conductivity and utilization efficiency of a certain amount of graphite as conductive additive to improve electrode can be also mixed.Graphite
Why material can be widely used in field of batteries, the advantage from its numerous protrusion, as chemical stability is good, abundant electricity follows
Ring excellent in stability, conductivity height, natural rich reserves, raw material supply abundant, cheap, green non-pollution etc..But stone
There is also can not be ignored negative electrode material of the ink material as lithium ion battery.For example, the lithium storage content of graphite cathode compared with
Low (320~350mAh g-1), and small (the theoretical capacity only 372mAh g in capacity boost space-1)；In battery charging, lithium ion
The solvent molecule of battery can be inserted into altogether graphite layers with lithium ion, cause graphite-structure variation and capacity attenuation.
Oxide material is another kind of widely used electrode active material.In lithium ion battery, cobalt acid lithium, phosphoric acid
Iron lithium, cobalt lithium nickel manganese oxide (ternary) positive electrode have been realized in Commercialization application at present.In terms of cathode, based on conversion reaction
The oxide-based negative electrode material such as iron oxide also shows very high reversible lithium storage capacity.But iron oxide material is a kind of exhausted
Edge body material, conductivity are very poor.It is anxious to will cause battery capacity under the conditions of high current charge-discharge using pure iron oxide as negative electrode material
Play decline, significantly reduces the multiplying power property (namely high-power output characteristic) of lithium ion battery.In addition, iron oxide cathode material exists
Reciprocal violent volume change can occur because of lithium ion insertion-deintercalation reaction when charge and discharge, material dusting, resistance is caused to increase
Greatly, capacity rapid decay, the serious promotion for restricting capacity of lithium ion battery.
It is said from the angle of material property, iron oxide cathode material and graphite cathode material have very strong complementarity.Thus,
Further to promote battery performance, researcher, which proposes, carries out iron oxide material and graphite material compound experiment conception.
Such as: the Chinese patent of application number 201711044838.0 disclose a kind of nano oxidized iron particle for lithium ion battery/
The preparation method of micro crystal graphite composite material is expanded, microcrystalline graphite material is carried out a high-temperature expansion by this method, is obtained primary
Expand micro crystal graphite；Then once to expand micro crystal graphite and ferrocene as raw material ball milling mixing, then secondary high-temperature expansion is carried out
Obtain nano oxidized iron particle/expansion micro crystal graphite composite material.The chemical property of graphite can be improved in above-mentioned modified method,
But method of modifying is complicated, needs by three step process；And the density of expanded graphite is very low, and volume capacity is small, very unfavorable
In the promotion of battery volume energy density.The Chinese patent of application number 201611009344.4 discloses a kind of 3D iron oxide/stone
The preparation method of black alkene combination electrode material, this method react to form iron-miaow with imidazolium compounds first with Fe source compound
Azoles frame compound, then calcining obtains iron oxide microballoon in air.By this iron oxide microballoon and graphite oxide ultrasonic disperse
Yu Shui is introduced after reducing agent redox graphene and is prepared iron oxide/graphite oxide aeroge using freeze-drying, then
3D iron oxide/graphene combination electrode material is obtained in inert atmosphere high-temperature calcination.The preparation method of the patent disclosure is using cold
The problems such as freeze-drying drying process, there are at high cost, the production cycle is long, yield is small.Also, due to the product density of graphite airsetting colloidal state
Very low, volume and capacity ratio is necessarily lower.
Summary of the invention
Graphite cathode material capacity is low, solvent is embedded in altogether to solve, and iron oxide cathode material conductivity is low, multiplying power property is poor
The problem of, the invention discloses a kind of novel graphite/oxide composite preparation methods.
To realize one of goal of the invention, technical scheme is as follows:
A kind of preparation method of carbon, iron oxide double-coating composite cathode material of silicon/carbon/graphite comprising the steps of:
A. FeO is preparedxSolid content is the FeO of 2.5-20% (weight)x/ alcohol dispersion liquid:
FeO is added into ball grinderx, abrading-ball and ethyl alcohol, the ball milling 1-24 hours shape under 200-500r/min speed conditions
At stable FeOx/ alcohol dispersion liquid；
B. polyethylene nitrile (PAN) coated graphite material is prepared:
The n,N-Dimethylformamide solution (DMF) that polyethylene nitrile concentration is 10-100g/L is configured, powdered graphite is added
Disperse to the n,N-Dimethylformamide solution, wherein the powdered graphite and the n,N-Dimethylformamide solution weight
Then amount stirs the centrifugation after powdered graphite is fully dispersed, filtering in 1-4 hour for the powdered graphite from molten than being 1:1-100
The graphite material coated to get PAN is separated in liquid；
C. graphite@PAN@FeO is preparedxMaterial:
The graphite material for the PAN cladding that step B is separated is added to the FeO of step A preparationxIt is stirred in/alcohol dispersion liquid
After 10-30 minutes, the graphite material surface of PAN cladding forms FeOxClad is then centrifuged for, filters to get graphite@PAN@
FeOxMaterial；
D. graphite@C@FeOxDouble-coating composite material:
By the resulting graphite@PAN@FeO of step CxMaterial high-temperature process 1-5 at inert atmosphere protection, 500-1500 DEG C
Hour, it then cools to room temperature to get graphite@C@FeOxDouble-coating composite material.
It is preferred that inert gas described in step D is one of nitrogen, argon gas, helium, hydrogen, methane, acetylene or several
Kind.
It is the two of realization goal of the invention, technical scheme is as follows:
The graphite@C@FeO that the above method preparesxMaterial.
It is the three of realization goal of the invention, technical scheme is as follows:
The graphite@C@FeOxThe application of material is used as negative electrode material in lithium ion battery.
Key of the invention is graphite@C@FeO prepared by the present inventionxThe C layer of material enhances graphite and iron oxide
Associativity, solvent molecule is inserted into graphite altogether when battery being prevented to charge, so that the cyclical stability of material is improved, and FeOx
Layer can be obviously improved the lithium storage content of resulting materials as high capacity active material.
Since the DMF solution of PAN has viscosity, one layer of solution clad, graphite surface adherency can be formed in graphite surface
DMF dissolve each other with ethyl alcohol, the PAN of graphite surface loses DMF solvent and is precipitated to form PAN clad (i.e. graphite@PAN)；It is same with this
When, the ferric oxide particles of existing lewis acidity to lewis base property PAN surface migration and are adsorbed in iron oxide alcohol dispersion liquid,
Interaction occurs for the two quickly in graphite@PAN area load iron oxide coated layer (graphite@PAN@FeOx), the graphite@
For PAN@FeOx after drying, high temperature cabonization processing, PAN carbonization is converted into Pyrolytic carbon coating, forms graphite@C@FeOx bilayer packet
Cover structure.
Graphite@C@FeOx double-coating material prepared by the present invention eliminates the solvent of the lithium ion battery in battery charging
The problem of molecule can be inserted into altogether graphite layers with lithium ion, and graphite-structure variation is caused largely to decay with capacity.Therefore, of the invention
The graphite@C@FeOx double-coating material of preparation has superior electric cyclical stability under the premise of not reducing specific capacity,
And graphite@C@FeOx double-coating structural chemistry stability is good, abundant electric cyclical stability is excellent, conductivity is high, raw material supplies
To abundant, cheap, green non-pollution.
Detailed description of the invention
Fig. 1 is the SEM photograph of graphite@C@Fe3O4 prepared by embodiment 1.
Fig. 2 is the SEM photograph of the Fe3O4 sample of comparative example 1-1 preparation.
Fig. 3 is the SEM photograph of comparative example 1-2 spherical graphite sample.
The cyclical stability for the graphite@C@Fe3O4 that Fig. 4 is Fe3O4 sample, prepared by spherical graphite sample, embodiment 1 is bent
Line.
Specific embodiment
The application is described in further detail with case study on implementation with reference to the accompanying drawing.It is understood that this place
The specific implementation case of description is used only for explaining related invention, rather than the restriction to the invention.It also should be noted that
For ease of description, part relevant to invention is illustrated only in attached drawing.
Embodiment 1:
Step A: by 2.5g Fe3O4, 20g aluminium oxide abrading-ball (diameter 5mm) and 50ml ethyl alcohol is added to 150ml ball grinder and works as
In, the ball milling 24 hours under the conditions of 500 revs/min filters off abrading-ball, obtains Fe3O4Alcohol dispersion liquid.
Step B: separately taking 50g PAN to be added in 1000ml DMF, and stirring makes PAN after completely dissolution in 3 hours, then Xiang Rong
15g powdered graphite is added in liquid and continues stirring 1 hour.Then, centrifugation separates graphite with the DMF solution of PAN, obtains mud
Shape graphite material (DMF solution that surface is coated with PAN).
Step C: under agitation, the muddy graphite material that step B is separated is evenly spread into step A preparation
Fe3O4In alcohol dispersion liquid；Above-mentioned dispersion liquid is sufficiently dry at 60 DEG C after continuing stirring 2 hours, obtains graphite@PAN@Fe3O4
Material.
Step D: by graphite@PAN@Fe obtained in step C3O4Nitrogen atmosphere in be warming up to 900 DEG C, keep the temperature 3h, it is natural
It is cooled to room temperature, graphite@C@Fe can be obtained3O4Composite negative pole material.
Graphite@C@Fe prepared by this example3O4Composite negative pole material tests electrochemistry as cathode assembling Symmetrical cells
Can, the material is in 0.01-3V (vs.Li/Li+) in potential range, specific capacity is about 560mAh/g (current density 200mA/g),
Capacity is still 560mAh/g after 200 circulations, and capacity retains the 100% of initial value.
Comparative example 1-1:
Step A: taking 10 grams of ferric nitrates and 2 grams of oxalic acid, 2 grams of ammonium nitrate to be dissolved in 40mL deionized water, stirs 15 minutes
After completely dissolution, above-mentioned dispersion liquid is transferred in alumina crucible and is evaporated for 105 DEG C.
Step B: will be evaporated sample and be put into 400 degree of electric furnaces and heat 30 minutes, cause the oxidation between ferric nitrate and oxalic acid
Reduction reaction can be obtained Fe after sample is cooled to room temperature3O4Sample.
Fe prepared by this example3O4Material tests chemical property as cathode assembling Symmetrical cells, and the material is in 0.01-
3V(vs.Li/Li+) in potential range, specific capacity is about 1190mAh/g (current density 200mA/g), capacity after 200 circulations
786mAh/g is decayed to, capacity retains the 66% of initial value.
Comparative example 1-2:
Negative electrode material directly is acted on using the spherical graphite of purchase, using graphite as cathode assembling Symmetrical cells test electrification
Performance is learned, in 0.01-3V (vs.Li/Li+) in potential range, the specific capacity for measuring spherical graphite is about that (electric current is close by 420mAh/g
Spend 200mA/g), for capacity attenuation to 300mAh/g, capacity retains the 71% of initial value after 200 circulations.
Graphite@PAN@Fe prepared by embodiment 13O4Fe in composite negative pole material and comparative example3O4Or graphite cathode material phase
Than specific capacity is about 560mAh/g (current density 200mA/g), and capacity is held essentially constant after 200 circulations, and embodiment 1 is made
Standby graphite@PAN@Fe3O4Composite negative pole material solves the problems, such as that graphite cathode material capacity is low, solvent is embedded in altogether, Fe3O4
The problem that negative electrode material conductivity is low, multiplying power property is poor,
Embodiment 2:
Step A: by 8g Fe3O4, 40g aluminium oxide abrading-ball (diameter 5mm) and 50ml ethyl alcohol is added to 150ml ball grinder and works as
In, the ball milling 5 hours under the conditions of 1000 revs/min filters off abrading-ball, obtains Fe3O4Alcohol dispersion liquid.
Step B: separately taking 100g PAN to be added in 1000ml DMF, and stirring makes PAN after completely dissolution in 3 hours, then to
24g powdered graphite is added in solution and continues stirring 1 hour.Then, centrifugation separates graphite with the DMF solution of PAN, obtains mud
Pulpous state graphite material (DMF solution that surface is coated with PAN).
Step C: under agitation, the muddy graphite material that step B is separated is evenly spread into step A preparation
Fe3O4In alcohol dispersion liquid；Above-mentioned dispersion liquid is sufficiently dry under the conditions of 60 DEG C after continuing stirring 2 hours, obtains graphite@PAN@
Fe3O4Material.
Step D: by graphite@PAN@Fe obtained in step C3O4Argon atmosphere in be warming up to 1300 DEG C, keep the temperature 1h, from
It is so cooled to room temperature, graphite@C@Fe can be obtained3O4Composite negative pole material.
Graphite@C@Fe prepared by this example3O4Composite negative pole material tests electrochemistry as cathode assembling Symmetrical cells
Can, the material is in 0.01-3V (vs.Li/Li+) in potential range, specific capacity is about 640mAh/g (current density 200mA/g),
Capacity is still 598mAh/g after 200 circulations, and capacity retains the 93% of initial value.
Embodiment 3:
Step A: by 1g Fe3O4, 20g aluminium oxide abrading-ball (diameter 5mm) and 50ml ethyl alcohol is added to 100ml ball grinder and works as
In, the ball milling 3 hours under the conditions of 800 revs/min filters off abrading-ball, obtains Fe3O4Alcohol dispersion liquid.
Step B: separately taking 25g PAN to be added in 1000ml DMF, and stirring makes PAN after completely dissolution in 3 hours, then Xiang Rong
10g graphite is added in liquid and continues stirring 1 hour.Then, centrifugation separates graphite with the DMF solution of PAN, obtains muddy stone
Ink material (DMF solution that surface is coated with PAN).
Step C: under agitation, the muddy graphite material that step B is separated is evenly spread into step A preparation
Fe3O4In alcohol dispersion liquid；Above-mentioned dispersion liquid is sufficiently dry under the conditions of 60 DEG C after continuing stirring 2 hours, obtains graphite@PAN@
Fe3O4Material.
Step D: by graphite@PAN@Fe obtained in step C3O4Argon atmosphere in be warming up to 600 DEG C, keep the temperature 5h, it is natural
It is cooled to room temperature, graphite@C@Fe can be obtained3O4Composite negative pole material.
Graphite@C@Fe prepared by this example3O4Composite negative pole material tests electrochemistry as cathode assembling Symmetrical cells
Can, the material is in 0.01-3V (vs.Li/Li+) in potential range, specific capacity is about 410mAh/g (current density 200mA/g),
Capacity is still 404mAh/g after 200 circulations, and capacity retains the 98% of initial value.
Above description is only the preferred embodiment of the application and the explanation to institute's application technology principle.Those skilled in the art
Member is it should be appreciated that invention scope involved in the application, however it is not limited to technology made of the specific combination of above-mentioned technical characteristic
Scheme, while should also cover in the case where not departing from the inventive concept, it is carried out by above-mentioned technical characteristic or its equivalent feature
Any combination and the other technical solutions formed.Such as features described above and disclosed herein but be not limited to similar functions
Technical characteristic replaced mutually and the technical solution that is formed.
Claims (4)
1. the preparation method of a kind of carbon, iron oxide double-coating composite cathode material of silicon/carbon/graphite, it is characterised in that comprise the steps of:
A. FeO is preparedxSolid content be 2.5-20%(weight) FeOx/ alcohol dispersion liquid:
FeO is added into ball grinderx, abrading-ball and ethyl alcohol, formed within ball milling 1-24 hours under 200-500 r/min speed conditions steady
Fixed FeOx/ alcohol dispersion liquid；
B. polyethylene nitrile (PAN) coated graphite material is prepared:
The n,N-Dimethylformamide solution that polyethylene nitrile concentration is 10-100g/L is configured, powdered graphite is added to the N,
Dinethylformamide solution dispersion, wherein the powdered graphite is 1 with the n,N-Dimethylformamide solution weight ratio:
Then 1-100 stirs the centrifugation after powdered graphite is fully dispersed, filtering in 1-4 hours and separates the powdered graphite from solution,
Up to the graphite material of PAN cladding；
C. graphite@PAN@FeO is preparedxMaterial:
The graphite material for the PAN cladding that step B is separated is added to the FeO of step A preparationx10-30 is stirred in/alcohol dispersion liquid
After minute, the graphite material surface of PAN cladding forms FeOxClad is then centrifuged for, filters to get graphite@PAN@FeOxMaterial
Material；
D. graphite@C@FeO is preparedxDouble-coating composite material:
By the resulting graphite@PAN@FeO of step CxMaterial is at inert atmosphere protection, 500-1500 DEG C after high-temperature process 1-5 hours
It is cooled to room temperature to get graphite@C@FeOxDouble-coating composite material.
2. preparation method according to claim 1, it is characterised in that inert atmosphere described in step D is nitrogen, argon gas, helium
Gas, hydrogen, methane, any one in acetylene.
3. the graphite@C@FeO of method preparation as claimed in claim 1 or 2xComposite material.
4. the application of graphite@C@FeOx composite material as claimed in claim 3, it is characterised in that the graphite@C@FeOx is multiple
Condensation material is used as negative electrode material application in lithium ion battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112563510A (en) * | 2020-12-10 | 2021-03-26 | 烟台大学 | Spherical graphite/manganese dioxide lithium battery negative electrode material and preparation method thereof |
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