CN106876705A - A kind of preparation method of fabricated in situ carbon/CNT coated lithium iron phosphate composite - Google Patents
A kind of preparation method of fabricated in situ carbon/CNT coated lithium iron phosphate composite Download PDFInfo
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- CN106876705A CN106876705A CN201710207321.2A CN201710207321A CN106876705A CN 106876705 A CN106876705 A CN 106876705A CN 201710207321 A CN201710207321 A CN 201710207321A CN 106876705 A CN106876705 A CN 106876705A
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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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Abstract
The present invention provides a kind of preparation method of fabricated in situ carbon/CNT coated lithium iron phosphate composite, is related to battery material technical field.Preparation method of the present invention is:Weigh raw material lithium source, iron powder, phosphate, carbon source；First by iron powder and phosphate ball milling, hydrogen peroxide is added；Add lithium source and carbon source obtain slurry, sintered under dry, reproducibility/inert gas shielding, you can；The present invention is prepared for carbon/CNT coated lithium iron phosphate composite using the method for fabricated in situ, and heat treatment time is short；Composite has carbon coating rate higher, and preferably, cycle performance and high rate performance are greatly improved for stable electrochemical property and uniformity, and whole preparation technology flow is simple, has the advantages that safe efficient, cheap and environmental protection.
Description
Technical field
The present invention relates to battery material technical field, it is related to a kind of fabricated in situ carbon/CNT coated LiFePO 4 for lithium ion batteries to answer
The preparation method of condensation material.
Background technology
LiFePO4 has that environment-friendly, safe, many merits such as have extended cycle life, it has also become current lithium ion is moved
Power battery industryization uses most wide positive electrode.But the relatively low electronic conductivity of LiFePO4 and lithium ion diffusion rate are led
Cause its high rate performance poor, seriously constrain the marketing operational capability of lithium iron phosphate dynamic battery.It is current main from following
Three aspects are modified treatment to LiFePO4.(1) LiFePO4 mixes conductive material or coated with conductive material etc. to improve material
The conductance of material；(2) nanoscale high-density spherical ferric lithium phosphate is prepared, material specific surface area is improved and is increased effective number of sites；(3)
The chemical property that impurity improves material is carried out to olivine-type LiFePO4.Can wherein be dropped by coated with conductive carbon material
Low interface conduction resistance, improves electric conductivity, while carbon material cladding can reduce lithium iron phosphate nano particle agglomeration, it is excellent
Embedding lithium performance improves electric discharge and the high rate performance of LiFePO4.Such as Wang etc. (Journal of Power Sources,
2013,233:43-46.) with FeSO4·7H2O、H3PO4With LiOH for raw material prepares presoma by coprecipitation, at calcining
Particle diameter is obtained after reason for 30~80nm, 0.1C and 10C specific capacities are respectively the LiFePO of 155 and 110mAh/g4/ C-material.Liu
Deng (Electrochimica Acta, 2010,55:4694-4699.) with FeSO4·7H2O、LiH2PO4With LiOH for raw material is super
Sonication filtering calcining is obtained the LiFePO of 50nm or so4/ C-material, itself 1C and 2C specific capacity is respectively 140 and 135mAh/g.
CNT (CNTs) has special tubular graphitic structure, and electrical conductivity is high, in addition the three-dimensional CNTs tools of oriented growth
There is excellent mechanical property, therefore CNTs has obtained extensive research as electrode material.(the Journal of Power such as Chen
Sources,2013,223:Hydro-thermal method 100-106.) is used by Fe (NO3)3、NH4H2PO4Treated different things alike with CNTs, UF membrane is dried
After obtain FePO4/ CNTs microballoons, then add LiOH mixing high-temperature calcinations to obtain LiFePO according to a certain percentage4/ CNTs microballoons,
The material has larger nano pore, the specific surface area and electrolyte permeability ability of material is improve, in high rate charge-discharge
When shows storage lithium ability very high, and (specific capacity reaches 155mAhcm during 5C rate charge-discharges-3) and cyclical stability (1000
Capacity is maintained at more than 90% after circle discharge and recharge).Composite prepared by the method, its tubulose CNTs and active material particle
Surface contact is simultaneously insufficient, (ACS Sustainable Chemistry＆Engineering, 2013,2 (2) so Liu etc.:
200-206.) consider that introducing nanoscale carbon black connects the two to improve the electrical conductivity of electrode material.Wherein carbon black (20~
60nm) particle provides the short distance electric transmission between lithium iron phosphate particles, and (30~100 μm) of CNTs provides one-dimensional leading
Electric network forms point to line style long-range conductive path so that LiFePO4 mixing material has preferably circulation conservation rate.But
CNTs is relatively weak with the binding ability of LiFePO4 as additive, is the adhesion for further improving material, can be in phosphoric acid
Iron lithium superficial growth CNTs or in CNTs superficial growth active materials.Wang etc. (Advanced Energy Materials,
2016,6(16):1600426.) with CNTs as core, Li+And Fe3+Because charge effect absorption is on CNTs surfaces, PO is added4 3-Water
Heat treatment forms Li3PO4、FePO4Grappling on the carbon nanotubes, C LiFePO is obtained after being processed through ultrasonic disperse carbon thermal reduction4/
CNTs composites.Material 0.2C multiplying power dischargings capacity is 155mAhg-1Far above C@LiFePO4141mAhg-1, together
When 10C discharge and recharges 1000 times after capacity keep 98%, cyclical stability is high.
These preparation methods reported are generally that the pretreatment such as first coprecipitation, hydro-thermal method carries out high temperature carbon reduction reaction again
Generation target product, although can well control pattern, the size of material, improve the electrical property of material, but such side
Method is complex due to technique, and equipment requirement is higher, and the cost such as divalence source of iron used, CNTs is of a relatively high, strongly limit product
Industry application, therefore a kind of process is simple, the method for preparing carbon/CNT coated lithium iron phosphate composite with low cost
Urgently excavate.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of fabricated in situ carbon/CNT coated LiFePO 4 for lithium ion batteries composite wood
The preparation method of material, solves carbon/CNT coated lithium iron phosphate composite preparation technology complexity, cost in the prior art
Technical problem high.
To realize object above, the present invention is achieved by the following technical programs:
A kind of preparation method of fabricated in situ carbon/CNT coated lithium iron phosphate composite, comprises the following steps:
S1, according to mol ratio Li:Fe:P:C is 1.02:0.8~1:1~1.5:0.08~0.18 weighs lithium source, iron powder, phosphorus
Hydrochlorate, carbon source；
S2, the iron powder by 300~800 mesh, ball-milling reaction is carried out 1~3 hour with phosphate, and it is 1~3 to control pH value of solution,
Hydrogen peroxide reaction is added to obtain Iron phosphate (FePO4) dihydrate ball milling liquid；
S3, lithium source and carbon source are added in Iron phosphate (FePO4) dihydrate ball milling liquid obtained in step S2, ball milling 3~8 hours
To slurry；
S4, slurry obtained in step S3 is obtained into ferric lithium phosphate precursor powder in 200~300 DEG C of spray drying；
S5, ferric lithium phosphate precursor powder obtained in step S4 is sintered under reproducibility/inert gas shielding, you can.
Preferably, the iron powder is reduced iron powder, weight of iron percentage composition >=98% of weight of iron percentage composition >=98%
Electrolytic iron powder, weight of iron percentage composition >=98% spheroidal graphite casting powder at least one.
Preferably, the phosphate is at least one in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus pentoxide.
Preferably, the lithium source is lithium carbonate, lithium hydroxide, lithium phosphate, the lithium of phosphoric acid hydrogen two, lithium dihydrogen phosphate, lithium nitrate
In at least one.
Preferably, the carbon source includes first kind carbon source, Equations of The Second Kind carbon source and the 3rd class carbon source, and wherein first kind carbon source is
At least one in glucose, maltose, rock sugar, fructose；Equations of The Second Kind carbon source is polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyvinyl alcohol contracting
At least one in butyraldehyde, polypyrrole；3rd class carbon source is at least one in cyanamide, dicyanodiamine, melamine.
Preferably, the inert gas is at least one in nitrogen, argon gas, helium.
Preferably, the reducibility gas are hydrogen that volume fraction is 0.5~1%.
Preferably, the step S5 is that obtained dry ferric lithium phosphate precursor powder is warming up into 200~600 DEG C of burnings
Knot 3~5 hours, 50~100 DEG C are water-cooled to using circulating cooling, then are warming up to 600~1100 DEG C and are sintered 5~15 hours, cold
But to room temperature, you can.
Preferably, the step S5 is that obtained dry ferric lithium phosphate precursor powder is warming up into 200~600 DEG C of burnings
Knot 3~5 hours, 50~100 DEG C are water-cooled to using circulating cooling, and this stage is sintered protection using pure inert gas；Again
It is warming up to 600~1100 DEG C to sinter 5~15 hours, this stage is sintered reduction protection using reproducibility/inert gas, cooling
To room temperature, you can.
Preferably, the 3rd class carbon source contains ammonium root, and ammonia is produced in sintering process, anti-with ammonia using phosphate
Ammonium dihydrogen phosphate should be obtained.
The present invention provides a kind of preparation method of carbon/CNT coated lithium iron phosphate composite, with prior art phase
It is than advantage:
The present invention is prepared for carbon/CNT coated lithium iron phosphate composite, the technique using the method for fabricated in situ
Method heat treatment time is short, easily accomplishes scale production；Carbon/CNT coated lithium iron phosphate composite has carbon higher
Clad ratio, stable electrochemical property and uniformity preferably, are remarkably improved the capacity of material, reduce irreversible capacity loss, carry
High circulation performance and high rate performance, whole preparation technology flow are simple, have the advantages that safe efficient, cheap and environmental protection；
In preparation method of the present invention, carbon source includes first kind carbon source, Equations of The Second Kind carbon source and the 3rd class carbon source, and calcination process is
Calcine by steps, in preparation process, in the range of 200~600 DEG C, lithium source and source of iron first carry out anaerobic sintering, and in aggregate
One class carbon source is by part Fe3+It is reduced to Fe2+, Equations of The Second Kind carbon source and carbon metaplasia is coated on particle surface, micro Fe into agraphitic carbon2+
It is catalyzed the 3rd class carbon source generation class graphite ene-type g-C3N4；In the range of 600~1100 DEG C, hydrogen is further by Fe3+It is reduced to
Fe2+, and gradually into karyogenesis olivine-type LiFePO4, while Fe2+-g-C3N4Pintsch process growth in situ forms carbon nanometer
Pipe, the preparation method can generate the carbon/CNT of stabilization, be conducive to raising carbon/CNT coated LiFePO 4 for lithium ion batteries to be combined
The cycle performance and high rate performance of material；
The relatively low source of iron of present invention selection price, control lithium, iron, phosphorus proportioning, optimizes organic and inorganic carbon source addition, real
Existing agraphitic carbon and CNT generation ratio controllable adjustment, improve carbon/CNT coated lithium iron phosphate composite synthesis
Conductance ability.Centrifugation rate is dried by adjustable spraying and gas flow temperature is imported and exported in control, efficiently can in batches prepare carbon/carbon nanometer
Pipe coated lithium iron phosphate composite presoma, presoma dried feed particle diameter is smaller and distribution is stable, is conducive to subsequent high temperature to forge
Burn grain crystalline.Segmented high-temperature protection calcining fabricated in situ loose network structure and the larger carbon of specific surface area/CNT bag
Cover composite ferric lithium phosphate material, it is ensured that agraphitic carbon and CNT normal growth, while carbon source is decomposed during Pintsch process,
Portion gas discharge promotes material to produce micropore, further improves electrolyte infiltration and lithium ion exchanged ability, lifting material electricity
Chemical property.Calcination process situ generates agraphitic carbon and CNT, improves conductive material glutinous with LiFePO4
Put forth effort and composite electronics conduction efficiency, lift the charge-discharge performance of positive electrode.
The carbon that preparation method of the present invention is obtained/CNT coated lithium iron phosphate composite is made with lithium piece as negative pole
CR2016 types button cell carry out charge-discharge test, 0.2C initial charges specific capacity is 155~160mAh/g, first coulomb effect
Rate 90~99%, averaged discharge specific capacity is 150~160mAh/g, and 1C averaged discharges specific capacity is 145~155mAh/g, circulation
50 circle specific capacities remain at more than 90%, show excellent electrochemical properties, are expected to be applied to electrokinetic cell field.
Brief description of the drawings
Fig. 1 is the N of fabricated in situ carbon/CNT coated lithium iron phosphate composite of the present invention2Adsorption/desorption figure and hole
Footpath distribution map；
Fig. 2 is fabricated in situ carbon/CNT coated lithium iron phosphate composite of the present invention in 0.2C and 1C discharge and recharges times
Electrical property curve map under rate.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, with reference to embodiment to the present invention
Technical scheme in embodiment is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented
Example, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creativeness
The every other embodiment obtained under the premise of work, belongs to the scope of protection of the invention.
Material makes button battery and the method for test material chemical property is as follows in embodiment:
(1) preparation of battery anode slice:By synthesized carbon/CNT coated lithium iron phosphate composite and binding agent
Kynoar (PVDF) is with mass ratio 8:2 weigh sample.Binding agent and organic solvent 1-METHYLPYRROLIDONE (NMP) are mixed
After dissolve, add carbon/CNT coated lithium iron phosphate composite be sufficiently stirred for into slurry, be coated in carbon-coated aluminum foils surface,
Roll-in obtains battery anode slice after drying.
(2) battery assembling and performance test:Carbon/CNT coated LiFePO 4 for lithium ion batteries is tested using CR2016 types button cell
The chemical property of composite.Positive plate after roll-in is struck out the positive plate of diameter 12mm, according to just after correct amount
Pole piece composition converses carbon/CNT coated lithium iron phosphate composite effective mass.Use the positive plate, electrolysis that prepare
Liquid, the PE barrier films of diameter 16mm, the lithium piece of diameter 15mm, assemble button cell in glove box.
(3) the specific capacity test of battery uses the new prestige battery test system in Shenzhen, and test temperature is 25 DEG C, and 0.2C and 1C fill
Discharge-rate respectively carries out 50 loop tests.
Embodiment 1:
The present embodiment fabricated in situ carbon/CNT coated lithium iron phosphate composite, comprises the following steps:
S1, weigh 10 part of 500 mesh iron powder and be added in 40 parts of phosphate and mix, control pH value of solution to carry out clipping the ball for 2.0
Mill 3 hours, is added dropwise over oxidant hydrogen peroxide and is persistently uniformly mixed, and treats blackish green Fe (H2PO4)3Solution colour is gradually moved back
Stop adding hydrogen peroxide generation Iron phosphate (FePO4) dihydrate insoluble matter.
S2, to added in above-mentioned two hypophosphite monohydrates insoluble matter 200 parts of water, 6 parts of lithium carbonates and 0.5 part of glucose, 0.5 part gather
Vinyl alcohol, 0.5 part of melamine mix 3 hours after ball-milling treatment 3 hours, rotating speed 500rpm is controlled, after the completion of ball milling
To milk yellow viscous paste；
S3, slurry drying treatment is carried out using Centrafugal spray drying tower, it is 350 DEG C, leaving air temp to control EAT
It it is 150 DEG C, atomizing disk rotating speed is 40000rpm, obtains the dried feed that particle diameter is about 15 μm, is ferric lithium phosphate precursor powder；
S4, the dried feed of preparation is put into ceramic crucible it is placed in tube furnace, is the nitrogen of 0.2L/min in gas flow
300 DEG C of constant temperature is risen to 3 hours with 2.5 DEG C/min heating rates in atmosphere, is cooled to after room temperature with 5 DEG C/min and is passed through the mixing of nitrogen hydrogen
Gas (99:1) 500 DEG C of constant temperature is warming up to 2 hours with 5 DEG C/min, then 800 DEG C of constant temperature is warming up to 5 hours with 2.5 DEG C/min, control
10 DEG C/min speed is down to after room temperature and closes gas and take out sintering sample naturally after being cooled to 200 DEG C, and sintering sample is fully ground
Can obtain the carbon/CNT coated lithium iron phosphate composite of fabricated in situ.
Fig. 1 is that fabricated in situ carbon/CNT coated lithium iron phosphate composite prepared by embodiment 1 is stepped on by U.S.'s health
NOVA2200e specific surface area analysis instrument detect the N for obtaining2Adsorption/desorption figure and graph of pore diameter distribution.The material specific surface area
About 17.2m2/ g, pore-size distribution is concentrated mainly on 3~15nm, and these micropores are conducive to electrolyte to infiltrate and lithium ion exchanged.
Fig. 2 is the fabricated in situ carbon/CNT coated lithium iron phosphate composite of the preparation of the present embodiment 1 by assembling knob
The charging and discharging capacity of button half-cell charging and discharging curve and the 50th circle under charging and discharging curve and 1C multiplying powers under the 0.2C multiplying powers
Variation diagram.As can be seen from the figure 0.2C specific discharge capacities are about 160mAh/g, and it is 99.02%, 1C that coulombic efficiency is circulated first
Averaged discharge specific capacity is about 148mAh/g, and specific capacity keeps 95% after 50 circulations, illustrates the carbon/CNT cladding phosphoric acid
Iron lithium composite material has good electrochemical properties, can use electrokinetic cell field.
Embodiment 2:
The present embodiment is identical with the preparation method of embodiment 1, differs only in:In synthesis carbon/CNT cladding phosphoric acid
Carbon source used is 0.6 part of glucose, 0.3 part of polyvinyl alcohol, 0.6 part of melamine during iron lithium composite material；Nitrogen atmosphere used
Thermostat temperature is 400 DEG C, and nitrogen hydrogen mixeding gas atmosphere thermostat temperature is 900 DEG C, and control agraphitic carbon and content of carbon nanotubes are obtained
To carbon/CNT coated lithium iron phosphate composite.
By the identical test mode of embodiment 1 to the present embodiment gained fabricated in situ carbon/CNT coated LiFePO 4 for lithium ion batteries
Composite carries out specific surface area analysis and Electrical Analysis, and carbon/CNT coated LiFePO 4 for lithium ion batteries prepared by the embodiment is answered
Condensation material specific surface area is more than embodiment 1.Electric performance test result is about 165mAh/g for 0.2C averaged discharge specific capacities, first
Circulation coulombic efficiency is about 150mAh/g for 98.11%, 1C averaged discharge specific capacities, and specific capacity keeps 91% after 50 circulations,
Illustrate that fabricated in situ carbon/CNT coated lithium iron phosphate composite prepared by the embodiment equally has good electrochemistry
Characteristic, can operate with electrokinetic cell field.
Embodiment 3:
The present embodiment is identical with the preparation method of embodiment 1, differs only in:In synthesis carbon/CNT cladding phosphoric acid
Carbon source used is 1 part of glucose, 0.2 part of polyvinyl alcohol, 0.3 part of melamine during iron lithium composite material；Nitrogen atmosphere liter used
Warm speed is 5 DEG C/min, and the unification of nitrogen hydrogen mixeding gas atmosphere heating rate is 5 DEG C/min, in order to control carbon/CNT to coat
The content ratio of agraphitic carbon and CNT, growth rate and shape characteristic in composite ferric lithium phosphate material.
By the identical test mode of embodiment 1 to the present embodiment gained fabricated in situ carbon/CNT coated LiFePO 4 for lithium ion batteries
Composite carries out specific surface area analysis and Electrical Analysis, and carbon/CNT coated LiFePO 4 for lithium ion batteries prepared by the embodiment is answered
Condensation material specific surface area is slightly less than embodiment 1.Too fast heating rate is unfavorable for porous generation, easily causes material morphology to collapse
Fall into.Electric performance test result is about 150mAh/g for 0.2C averaged discharge specific capacities, and it is 95.20% that coulombic efficiency is circulated first,
1C averaged discharge specific capacities are about 146mAh/g, and specific capacity keeps 92% after 50 circulations, illustrate original position prepared by the embodiment
Synthesis carbon/CNT coated lithium iron phosphate composite equally has good electrochemical properties, can operate with electrokinetic cell
Field.
Embodiment 4:
The present embodiment is identical with the preparation method of embodiment 1, differs only in:In synthesis carbon/CNT cladding phosphoric acid
Carbon source used is 0.5 part of sucrose, 0.5 part of polypyrrole, 0.5 part of dicyanodiamine during iron lithium composite material；Lithium source used is 3 parts of hydrogen-oxygens
Change lithium and 3 parts of lithium phosphate mixtures；Slurry ball-milling treatment 6 hours, controls rotating speed 800rpm, 3 μm of left sides of slurry granularity D50 reductions
It is right；Nitrogen atmosphere constant temperature time increases to 5 hours, and the nitrogen hydrogen mixeding gas atmosphere cryogenic thermostat time increases to 5 hours, high-temperature constant
The warm time increases to 10 hours.
By the identical test mode of embodiment 1 to the present embodiment gained fabricated in situ carbon/CNT coated LiFePO 4 for lithium ion batteries
Composite carries out specific surface area analysis and Electrical Analysis, and carbon/CNT coated LiFePO 4 for lithium ion batteries prepared by the embodiment is answered
Condensation material specific surface area is less than embodiment 1.Calcination time is long to cause material burning, causes material space to collapse.Electric performance test
Result is about 148mAh/g for 0.2C averaged discharge specific capacities, and it is 94.00%, 1C averaged discharge specific volumes that coulombic efficiency is circulated first
Amount is about 145mAh/g, and specific capacity keeps 90% after 50 circulations, illustrates fabricated in situ carbon/CNT prepared by the embodiment
Coated lithium iron phosphate composite equally has good electrochemical properties, can operate with electrokinetic cell field.
Embodiment 5:
The present embodiment is identical with the preparation method of embodiment 3, differs only in:The lithium source of addition is 2 parts of lithium dihydrogen phosphates
With 5 parts of lithium carbonates, more lithium sources are provided to prepare rich lithium material；Slurry ball-milling treatment 5 hours, it is 800rpm to control rotating speed；
High temperature sintering stage all heating rates are all controlled to 2.5 DEG C/min, reduce influence of the heating rate to material morphology.
By the identical test mode of embodiment 1 to the present embodiment gained fabricated in situ carbon/CNT coated LiFePO 4 for lithium ion batteries
Composite carries out specific surface area analysis and Electrical Analysis, and carbon/CNT coated LiFePO 4 for lithium ion batteries prepared by the embodiment is answered
Condensation material specific surface area is slightly larger than embodiment 1, and slower heating rate is conducive to glucose, polyvinyl alcohol carbonization and melamine
Amine in-situ preparation CNT under the catalysis of trace iron powder.Electric performance test result is about for 0.2C averaged discharge specific capacities
165mAh/g, circulates coulombic efficiency for 98.10%, 1C averaged discharge specific capacities are about 155mAh/g first, compares after 50 circulations
Capacity keeps 93%, illustrates that fabricated in situ carbon/CNT coated lithium iron phosphate composite prepared by the embodiment equally has
There are good electrochemical properties, can operate with electrokinetic cell field
Embodiment 6:
A kind of preparation method of fabricated in situ carbon/CNT coated lithium iron phosphate composite, comprises the following steps:
S1, according to mol ratio Li:Fe:P:C is 1.02:0.9:1.2:0.13 weighs lithium source, iron powder, phosphate, carbon source；
S2,600 mesh iron powders and phosphate are carried out into ball-milling reaction 2 hours, it is 2 to control pH value of solution, adds hydrogen peroxide reaction
Iron phosphate (FePO4) dihydrate ball milling liquid is obtained, pH value of solution is 2, can fully dissolve iron powder, while effectively suppressing follow-up ferric phosphate hydrolysis life
Into ferric hydroxide precipitate；
S3, lithium source and carbon source are added in Iron phosphate (FePO4) dihydrate ball milling liquid obtained in step S2, ball milling is starched for 6 hours
Material；
S4, slurry obtained in step S3 is obtained into ferric lithium phosphate precursor powder in 250 DEG C of spray drying；
S5, dry ferric lithium phosphate precursor powder obtained in step S4 is warming up to 400 DEG C sinters 4 hours, using following
Ring cooling is water-cooled to 80 DEG C, and this stage is sintered protection using pure inert gas, and inert gas is nitrogen, argon gas, helium
Mix；It is warming up to 850 DEG C again to sinter 10 hours, this stage is sintered reduction protection using reproducibility/inert gas, lazy
Property gas be nitrogen, reducibility gas are the hydrogen that volume fraction is 0.8%, are cooled to room temperature, you can.
Wherein, iron powder is the spheroidal graphite casting powder of weight of iron percentage composition >=98%；Phosphate is phosphoric acid, ammonium dihydrogen phosphate, phosphorus
The ammonium of sour hydrogen two is mixed；Lithium source is lithium carbonate, lithium hydroxide, lithium phosphate, the lithium of phosphoric acid hydrogen two are mixed；Carbon source includes first
Class carbon source, Equations of The Second Kind carbon source and the 3rd class carbon source, wherein first kind carbon source are glucose；Equations of The Second Kind carbon source is polyvinyl alcohol；The
Three class carbon sources are cyanamide, dicyanodiamine, melamine are mixed；Contain ammonium root in the carbon source that the method is added, in high temperature
The waste gas such as ammonia can be produced in sintering process, carrying out acid-base neutralization treatment using certain density phosphate can obtain biphosphate
Ammonium, can use as raw material after purification, protect production environment, reduce production cost.In the range of 200~600 DEG C, lithium source and iron
Source first carries out anaerobic sintering, and the first kind carbon source in aggregate is by part Fe3 +It is reduced to Fe2 +, Equations of The Second Kind carbon source and carbon metaplasia is into nothing
Sizing carbon coating is in particle surface, micro Fe2 +It is catalyzed the 3rd class carbon source generation class graphite ene-type g-C3N4；At 600~1100 DEG C
In the range of, hydrogen is further by Fe3 +It is reduced to Fe2 +, Fe2 +-g-C3N4Pintsch process growth in situ forms CNT, while carbon
Nanotube can limit LiFePO4Crystallization direction and size.
Fabricated in situ carbon/CNT coated lithium iron phosphate composite obtained in the present embodiment according to embodiment method
Battery is made, 150mAh/g is not less than in 0.2C specific discharge capacities, 1C specific discharge capacities are not less than 145mAh/g, after 50 circulations
Specific capacity still keeps 90%.
Fabricated in situ carbon/CNT coated lithium iron phosphate composite graininess spherical in shape obtained by the present embodiment, forges
Imitation frosted glass is by D50 after pulverization process<1.0μm、D100<3.0 μm, these little particles are coated by more tiny carbon/CNT
Composite ferric lithium phosphate material nano particle constitute, size in 100~150nm or so, in nanometer range the material show compared with
For obvious nano aperture is distributed, the micropore on carbon/CNT is that electrolyte and lithium ion exchanged provide capillary channel, is carried
The chemical property of LiFePO 4 material high.
Embodiment 7:
A kind of preparation method of fabricated in situ carbon/CNT coated lithium iron phosphate composite, comprises the following steps:
S1, according to mol ratio Li:Fe:P:C is 1.02:0.8:1:0.08 weighs lithium source, iron powder, phosphate, carbon source；
S2,300 mesh iron powders and phosphate are carried out into ball-milling reaction 1 hour, it is 1 to control pH value of solution, adds hydrogen peroxide reaction
Iron phosphate (FePO4) dihydrate ball milling liquid is obtained, pH value of solution is 1, can fully dissolve iron powder, while effectively suppressing follow-up ferric phosphate hydrolysis life
Into ferric hydroxide precipitate；
S3, lithium source and carbon source are added in Iron phosphate (FePO4) dihydrate ball milling liquid obtained in step S2, ball milling is starched for 3 hours
Material；
S4, slurry obtained in step S3 is obtained into ferric lithium phosphate precursor powder in 200 DEG C of spray drying；
S5, dry ferric lithium phosphate precursor powder obtained in step S4 is warming up to 200 DEG C sinters 3 hours, using following
Ring cooling is water-cooled to 50 DEG C, and this stage is sintered protection using pure inert gas, and inert gas is argon gas；It is warming up to again
600 DEG C sinter 5 hours, and this stage is sintered reduction protection using reproducibility/inert gas, and inert gas is argon gas, reduction
Property gas is the hydrogen that volume fraction is 0.5%, is cooled to room temperature, you can.
Wherein, iron powder is the reduced iron powder of weight of iron percentage composition >=98%；Phosphate is phosphoric acid, ammonium dihydrogen phosphate, phosphorus
The ammonium of sour hydrogen two is mixed；Lithium source is lithium carbonate, lithium hydroxide, lithium phosphate, the lithium of phosphoric acid hydrogen two are mixed；Carbon source includes first
Class carbon source, Equations of The Second Kind carbon source and the 3rd class carbon source, wherein first kind carbon source are glucose, maltose, rock sugar are mixed；Second
Class carbon source is polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyvinyl butyral resin are mixed；3rd class carbon source be cyanamide, dicyanodiamine,
Melamine is mixed.
Embodiment 8:
A kind of preparation method of fabricated in situ carbon/CNT coated lithium iron phosphate composite, comprises the following steps:
S1, according to mol ratio Li:Fe:P:C is 1.02:1:1.5:0.18 weighs lithium source, iron powder, phosphate, carbon source；
S2,800 mesh iron powders and phosphate are carried out into ball-milling reaction 3 hours, it is 3 to control pH value of solution, adds hydrogen peroxide reaction
Iron phosphate (FePO4) dihydrate ball milling liquid is obtained, pH value of solution is 3, can fully dissolve iron powder, while effectively suppressing follow-up ferric phosphate hydrolysis life
Into ferric hydroxide precipitate；
S3, lithium source and carbon source are added in Iron phosphate (FePO4) dihydrate ball milling liquid obtained in step S2, ball milling is starched for 8 hours
Material；
S4, slurry obtained in step S3 is obtained into ferric lithium phosphate precursor powder in 300 DEG C of spray drying；
S5, dry ferric lithium phosphate precursor powder obtained in step S4 is warming up to 600 DEG C sinters 5 hours, using following
Ring cooling is water-cooled to 100 DEG C, and this stage is sintered protection using pure inert gas, and inert gas is helium；It is warming up to again
1100 DEG C sinter 15 hours, and this stage is sintered reduction protection using reproducibility/inert gas, and inert gas is helium, also
Originality gas is the hydrogen that volume fraction is 1%, is cooled to room temperature, you can.
Wherein, iron powder is the spheroidal graphite casting powder of weight of iron percentage composition >=98%；Phosphate is ammonium dihydrogen phosphate；Lithium source is phosphorus
The lithium of sour hydrogen two；Carbon source includes first kind carbon source, Equations of The Second Kind carbon source and the 3rd class carbon source, and wherein first kind carbon source is fructose；Second
Class carbon source is polypyrrole；3rd class carbon source is dicyanodiamine.
In sum, the present invention is prepared for carbon/CNT coated LiFePO 4 for lithium ion batteries composite wood using the method for fabricated in situ
Material, the process heat treatment time is short, easily accomplishes scale production；Carbon/CNT coated lithium iron phosphate composite tool
There is a carbon coating rate higher, stable electrochemical property and uniformity is preferably is remarkably improved the capacity of material, reduces irreversible appearance
Amount loss, improves cycle performance and high rate performance, and whole preparation technology flow is simple, with safe efficient, cheap and green ring
The advantages of guarantor.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention has been described in detail, it will be understood by those within the art that:It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent to which part technical characteristic；And these modification or
Replace, do not make the spirit and scope of the essence disengaging various embodiments of the present invention technical scheme of appropriate technical solution.
Claims (10)
1. a kind of preparation method of fabricated in situ carbon/CNT coated lithium iron phosphate composite, it is characterised in that including with
Lower step:
S1, according to mol ratio Li:Fe:P:C is 1.02:0.8~1:1~1.5:0.08 ~ 0.18 weighs lithium source, iron powder, phosphate, carbon
Source；
S2, the iron powder by 300 ~ 800 mesh, ball-milling reaction is carried out 1 ~ 3 hour with phosphate, and it is 1 ~ 3 to control pH value of solution, adds dioxygen
Water reaction obtains Iron phosphate (FePO4) dihydrate ball milling liquid；
S3, lithium source and carbon source are added in Iron phosphate (FePO4) dihydrate ball milling liquid obtained in step S2, ball milling is starched for 3 ~ 8 hours
Material；
S4, slurry obtained in step S3 is obtained into ferric lithium phosphate precursor powder in 200 ~ 300 DEG C of spray drying；
S5, ferric lithium phosphate precursor powder obtained in step S4 is sintered under reproducibility/inert gas shielding, you can.
2. preparation method according to claim 1, it is characterised in that:The iron powder is weight of iron percentage composition >=98%
In reduced iron powder, the electrolytic iron powder of weight of iron percentage composition >=98%, the spheroidal graphite casting powder of weight of iron percentage composition >=98% at least
It is a kind of.
3. preparation method according to claim 1, it is characterised in that:The phosphate is phosphoric acid, ammonium dihydrogen phosphate, phosphoric acid
At least one in the ammonium of hydrogen two, phosphorus pentoxide.
4. preparation method according to claim 1, it is characterised in that:The lithium source is lithium carbonate, lithium hydroxide, phosphoric acid
At least one in lithium, the lithium of phosphoric acid hydrogen two, lithium dihydrogen phosphate, lithium nitrate.
5. preparation method according to claim 1, it is characterised in that:The carbon source includes first kind carbon source, Equations of The Second Kind carbon
Source and the 3rd class carbon source, wherein first kind carbon source are at least one in glucose, maltose, rock sugar, fructose；Equations of The Second Kind carbon source
It is at least one in polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyvinyl butyral resin, polypyrrole；3rd class carbon source is cyanamide, dicyan
At least one in diamines, melamine.
6. preparation method according to claim 1, it is characterised in that:The inert gas is in nitrogen, argon gas, helium
It is at least one.
7. preparation method according to claim 1, it is characterised in that:The reducibility gas are that volume fraction is 0.5 ~ 1%
Hydrogen.
8. preparation method according to claim 1, it is characterised in that:The step S5 is by obtained dry ferric phosphate
Lithium presoma powder is warming up to 200 ~ 600 DEG C and sinters 3 ~ 5 hours, is water-cooled to 50 ~ 100 DEG C using circulating cooling, then be warming up to
600 ~ 1100 DEG C sinter 5 ~ 15 hours, are cooled to room temperature, you can.
9. preparation method according to claim 8, it is characterised in that:The step S5 is by obtained dry ferric phosphate
Lithium presoma powder is warming up to 200 ~ 600 DEG C and sinters 3 ~ 5 hours, and 50 ~ 100 DEG C are water-cooled to using circulating cooling, this stage profit
Protection is sintered with pure inert gas；It is warming up to 600 ~ 1100 DEG C again to sinter 5 ~ 15 hours, this stage utilizes reproducibility/inertia
Gas is sintered reduction protection, is cooled to room temperature, you can.
10. preparation method according to claim 5, it is characterised in that:The 3rd class carbon source contains ammonium root, sintered
Ammonia is produced in journey, ammonium dihydrogen phosphate is obtained using phosphate and ammonia reaction.
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| CN109167027A (en) * | 2018-08-20 | 2019-01-08 | 合肥国轩电池材料有限公司 | A kind of redox graphene/carbon coating/composite ferric lithium phosphate material preparation method |
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