CN106848222A - A kind of preparation method of LiFePO4/bis- carbon-coating clad composite material - Google Patents
A kind of preparation method of LiFePO4/bis- carbon-coating clad composite material Download PDFInfo
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- CN106848222A CN106848222A CN201710035890.3A CN201710035890A CN106848222A CN 106848222 A CN106848222 A CN 106848222A CN 201710035890 A CN201710035890 A CN 201710035890A CN 106848222 A CN106848222 A CN 106848222A
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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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- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention provides a kind of preparation method of LiFePO4/bis- carbon-coating clad composite material, comprises the following steps：Step one：Prepare the amount of certain material than source of iron, phosphorus source and lithium source, add reducing agent simultaneously to dissolve, add mesoporous carbon, and carry out ultrasonic agitation；Step 2：Mixed liquor obtained in step one is transferred in reactor, hydro-thermal reaction, room temperature is cooled to after reaction, product is scrubbed, composite is obtained after forced air drying；Step 3：Composite is placed in tube furnace, after carrying out first time high-temperature calcination, cooling is taken out, washing, drying；Step 4：Additive is taken to be dissolved in absolute ethyl alcohol; add the composite obtained by step 3; the second mixed liquor is configured to after agitated; second mixed liquor is placed in baking oven and is dried; by solvent evaporating completely; the product of gained carries out second high-temperature calcination under being placed in the protection of inert gas, and cooling, washing and drying are obtained the LiFePO4/bis- carbon-coating clad composite material of secondary granulation.
Description
【Technical field】
The present invention relates to battery material technical field, more particularly to a kind of LiFePO4/bis- carbon-coating clad composite material
Preparation method.
【Background technology】
LiFePO4 (LiFePO4) as the positive electrode of lithium-ion-power cell, with raw material sources are wide, nontoxic, reason
By specific capacity (170mAh/g) high, have extended cycle life, have a safety feature the advantages of, but, LiFePO4 lithium ion in itself expands
Scattered coefficient is low, and electron conductivity is poor, and capacitance loss is serious during low-temperature working, hinders further using for its.
At present, the improvement for LiFePO4 cryogenic property mainly has three aspects：First, surface is modified, in material crystals
The excellent electronic conductor of Surface coating (such as carbon, metal, metal oxide, conducting polymer) or fast-ionic conductor (pyrophosphoric acid
Lithium), to lift the transmission of ion or electronics on material crystals surface, so as to improve the chemical property of material；2nd, body phase is mixed
Miscellaneous, the bulk phase-doped band gap width for reducing material strengthens the electron conduction of body phase, on the other hand induction distortion of lattice, improves
Diffusion rate of the lithium ion in intracell；3rd, topography optimization, the main purpose of topography optimization is to increase reaction active site
Point, shortening lithium ion diffusion length, increase material tap density etc..
However, due to the particle diameter of lithium iron phosphate particles, microscopic appearance, crystal structure, doping and cladding material species and
The factors such as content, it is difficult to reach ideal effect by single improved method, when such as carbon coating improves LiFePO4, obtain equal
First, complete carbon coating layer is relatively difficult, and individual layer carbon coating, phosphorus content is relatively low, and the electron conduction effect of material is paid no attention to
Think.
In consideration of it, it is real be necessary to provide a kind of preparation method of new LiFePO4/bis- carbon-coating clad composite material with
Overcome disadvantages described above.
【The content of the invention】
It is an object of the invention to provide it is a kind of can improve battery cryogenic property, prevent from reuniting between particle, the particle diameter of particle
The preparation method of the big LiFePO4 of small, material surface area/bis- carbon-coating clad composite material.
To achieve these goals, the present invention provides a kind of preparation method of LiFePO4/bis- carbon-coating clad composite material,
Comprise the following steps：Step one：Prepare the amount of certain material than source of iron, phosphorus source and lithium source, uniform mixing, add reducing agent simultaneously
Dissolving, adds mesoporous carbon, and carries out ultrasonic agitation, and the first mixed liquor is obtained；Step 2：By the first mixing obtained in step one
Liquid is transferred in reactor, carries out hydro-thermal reaction, and room temperature is cooled to after reaction, and product is scrubbed, be obtained after forced air drying
The composite of lithium iron phosphate/carbon doping；Step 3：The composite of lithium iron phosphate/carbon doping obtained in step 2 is placed in
In tube furnace, under the protection of inert gas, after carrying out first time high-temperature calcination, cooling is taken out, and washing, drying are obtained primary phosphoric acid
Iron lithium/bis- carbon-coating clad composite material；Step 4：The additive for taking certain mass is dissolved in absolute ethyl alcohol, adds step 3 institute
Obtained primary LiFePO4/bis- carbon-coating clad composite material, it is agitated after be configured to the second mixed liquor, the second mixed liquor is put
Dried in baking oven, by solvent evaporating completely, the product of gained carries out second high-temperature calcination under being placed in the protection of inert gas,
Cooling, washing and drying are obtained the LiFePO4/bis- carbon-coating clad composite material of secondary granulation.
In a preferred embodiment, the reducing agent in the step one is glucose, citric acid, ascorbic acid, wheat
One or more of bud sugar.
In a preferred embodiment, the phosphorus source in the step one is H3PO4、NH4H2PO4In one or more.
In a preferred embodiment, the temperature of hydro-thermal reaction is 120-180 DEG C in the step 2, during hydro-thermal reaction
Between be 6~12h.
In a preferred embodiment, the temperature of the first time high-temperature calcination in the step 3 is 700~800 DEG C,
The time of high-temperature calcination is 2~6h.
In a preferred embodiment, the solid content of the second mixed liquor in the step 4 is 3wt%-10wt%.
In a preferred embodiment, the temperature of second high-temperature calcination in the step 4 is 400~600 DEG C,
The time of high-temperature calcination is 2~4h.
In a preferred embodiment, the additive in the step 4 is PVA (polyvinyl alcohol), PEG (poly- second two
Alcohol), one or more in PVP (polyvinylpyrrolidone).
In a preferred embodiment, also including step 5：Binding agent and oil-based solvent are added into double planetary mixer
Middle stirring 1-2h is dispersed, scraper；Conductive agent A and conductive agent B is added, 0.5-1h is dispersed for stirring, scraper；Add step
The LiFePO4 of the secondary granulation obtained by four/bis- carbon-coating clad composite material, disperses at a high speed 2-3h.
In a preferred embodiment, the binding agent in the step 5 is Kynoar binding agent；Described oil
Property solvent be 1-METHYLPYRROLIDONE；The conductive agent A is conductive black Super-P (SP), and conductive agent B is KS-6, carbon nanometer
Pipe (CNT), carbon nano-fiber (VGCF), one or more in Ketjen black (ECP).
The preparation method of the LiFePO4/bis- carbon-coating clad composite material provided compared to prior art, the present invention, passes through
HTHP Hydrothermal Synthesiss will be carried out in lithium source, phosphorus source, source of iron presoma " cast " to the three-dimensional nano space of meso-porous carbon material
LiFePO4, material grows in mesoporous carbon multidimensional duct, is conducive to controlling the size of material, reduces material primary particle size, increases
Bigger serface, shortens lithium ion mobility distance, for lithium ion mobility provides enough passages, improves material simultaneous with electrolyte
Capacitive；Using organic reducing substances such as glucose as secondary carbon source, ferrous ion can be prevented to be oxidized in reaction system,
After through high-temperature calcination, the composite ferric lithium phosphate material of double carbon coating layers is obtained, improve the electronic conductivity of material, improve battery
Low temperature charge-discharge performance and low-temperature circulating performance；And secondary granulation is carried out to material, increases the aggregate particle size of material, it is to avoid make
With nanometer technology be beaten, shorten mashing timeliness, save nanometer beating process used by dispersant, reduce battery make raw material into
Sheet and process costs, increase economic efficiency.
【Brief description of the drawings】
Fig. 1 is the SEM figures of traditional lithium iron phosphate/carbon covering material；
Fig. 2 is the SEM figures of the LiFePO4/bis- carbon-coating clad composite material prepared by the embodiment of the present invention 1；
Fig. 3 be the battery A that is made of traditional lithium iron phosphate/carbon covering material with the embodiment of the present invention 1 be obtained LiFePO4/bis-
- 20 DEG C of charging performance curve maps of the battery B made by carbon-coating clad composite material；
Fig. 4 be the battery A that is made of traditional lithium iron phosphate/carbon covering material with the embodiment of the present invention 1 be obtained LiFePO4/bis-
- 20 DEG C of discharge performance curve maps of the battery B made by carbon-coating clad composite material；
Fig. 5 be the battery A that is made of traditional lithium iron phosphate/carbon covering material with the embodiment of the present invention 1 be obtained LiFePO4/bis-
The cycle performance curve map of -20 DEG C of battery B made by carbon-coating clad composite material.
【Specific embodiment】
In order that the purpose of the present invention, technical scheme and Advantageous Effects become apparent from understanding, below in conjunction with accompanying drawing and
Specific embodiment, the present invention will be described in further detail.It should be appreciated that the specific implementation described in this specification
Mode is not intended to limit the present invention just for the sake of explaining the present invention.
The present invention provides a kind of preparation method of LiFePO4/bis- carbon-coating clad composite material, comprises the following steps：
Step one：Prepare the amount of certain material than source of iron, phosphorus source and lithium source, uniform mixing, add reducing agent simultaneously to dissolve,
Mesoporous carbon (CMK-3) is added, and carries out ultrasonic agitation, the first mixed liquor is obtained；
Step 2：First mixed liquor obtained in step one is transferred in reactor, hydro-thermal reaction is carried out, cooled down after reaction
To room temperature, product is scrubbed, the composite of lithium iron phosphate/carbon doping is obtained after forced air drying；
Step 3：The composite of lithium iron phosphate/carbon doping obtained in step 2 is placed in tube furnace, inert gas
Under protection, after carrying out first time high-temperature calcination, cooling is taken out, and washing, drying are obtained primary LiFePO4/bis- carbon-coating covered composite yarn
Material；
Step 4：The additive for taking certain mass is dissolved in absolute ethyl alcohol, adds the primary ferric phosphate obtained by step 3
Lithium/bis- carbon-coating clad composite material, it is agitated after be configured to the second mixed liquor, by the second mixed liquor be placed in baking oven dry, will
Solvent evaporating completely, the product of gained carries out second high-temperature calcination, cooling, washing and drying under being placed in the protection of inert gas
LiFePO4/bis- carbon-coating the clad composite material of secondary granulation, i.e. final LiFePO4/bis- carbon prepared by the present invention is obtained
Layer clad composite material.
Specifically, the ratio between substance withdrawl syndrome of source of iron, phosphorus source and lithium source in the step one is 1：1：3 or 1：1：2.
Specifically, the reducing agent in the step one is glucose, citric acid, ascorbic acid, one kind of maltose or many
Kind.
Specifically, the phosphorus source in the step one is H3PO4、NH4H2PO4In one or more.
Specifically, the temperature of hydro-thermal reaction is 120-180 DEG C in the step 2, the hydro-thermal reaction time is 6~12h.
Specifically, the inert gas in the step 3 is nitrogen；Inert gas in the step 4 is nitrogen.
Specifically, the temperature of the first time high-temperature calcination in the step 3 is 700~800 DEG C, the time of high-temperature calcination
It is 2~6h.
Specifically, the solid content of the second mixed liquor in the step 4 is 3wt%-10wt%.
Specifically, the temperature of second high-temperature calcination in the step 4 is 400~600 DEG C, the time of high-temperature calcination
It is 2~4h.
Specifically, the additive in the step 4 is PVA (polyvinyl alcohol), PEG (polyethylene glycol), PVP (polyethylene pyrroles
Pyrrolidone) in one or more.
Further, the preparation method of LiFePO4/bis- carbon-coating clad composite material that the present invention is provided also includes step
Five：Stirring 1-2h is dispersed during binding agent and oil-based solvent are added into double planetary mixer, and scraper is obtained positive pole glue；To
Conductive agent A and conductive agent B is added in positive pole glue, 0.5-1h is dispersed for stirring, scraper；Add secondary obtained by step 4
The LiFePO4 of granulation/bis- carbon-coating clad composite material, dispersion 2-3h, is obtained anode sizing agent at a high speed.
Specifically, binding agent in the step 5 be HSV900,5130 or equal Kynoar binding agent；It is described
Oil-based solvent be 1-METHYLPYRROLIDONE (NMP).Specifically, the solid content of the positive pole glue is 5-12%.
Specifically, the conductive agent A be conductive black Super-P (SP), conductive agent B be KS-6, CNT (CNT),
One or more in carbon nano-fiber (VGCF), Ketjen black (ECP).
Embodiment 1：
1st, the amount concentration ratio for preparing material is 1：1：3 FeSO4·H2O, H3PO4And LiOH, beaker is mixed into equal volume
In, 1.8g glucose is added under magnetic agitation, add 1.25g mesoporous carbon CMK-3s, ultrasonic agitation 30min to be allowed to uniform after dissolving
Dispersion.
2nd, the dispersed solution of step 1 gained is transferred in reactor, the hydro-thermal reaction 8h at 130 DEG C, reaction
After be cooled to room temperature, product is scrubbed, after forced air drying lithium iron phosphate/carbon doped and compounded material.
3rd, the lithium iron phosphate/carbon doped and compounded material for obtaining step 2 is placed in tube furnace, and under nitrogen protection, 750 DEG C high
Temperature calcining 2h after, cooling take out, with deionized water and absolute ethanol washing for several times after, dry to obtain primary LiFePO4/bis- carbon-coating
Clad composite material.
4th, weigh 2.0g PVA to be dissolved in absolute ethyl alcohol, the primary LiFePO4/bis- carbon-coating cladding for being subsequently added preparation is multiple
Condensation material, is configured to the slurry of 5wt%-10wt%, solution is placed in 90 DEG C of baking ovens after stirring at room temperature is dried, and solvent is complete
Full volatilization, subsequent product under nitrogen protection in 400~600 DEG C of 2~4h of high-temperature calcination, take out by cooling, deionized water washing number
After secondary, dry secondary granulation LiFePO4/bis- carbon-coating clad composite material.
Embodiment 2：
1st, the amount concentration ratio for preparing material is 1：1：3 FeSO4·H2O, H3PO4And LiOH, beaker is mixed into equal volume
In, 2.1g citric acids are added under magnetic agitation, add 1.50g mesoporous carbon CMK-3s, ultrasonic agitation 30min to be allowed to uniform after dissolving
Dispersion.
2nd, the dispersed solution of step 1 gained is transferred in reactor, the hydro-thermal reaction 10h at 150 DEG C, reaction
After be cooled to room temperature, product is scrubbed, after forced air drying lithium iron phosphate/carbon doped and compounded material.
3rd, the lithium iron phosphate/carbon doped and compounded material for obtaining step 2 is placed in tube furnace, and under nitrogen protection, 750 DEG C high
After temperature calcining 4h, cooling is taken out, with deionized water and absolute ethanol washing for several times after, dry to obtain LiFePO4/bis- carbon-coating cladding
Composite.
4th, weigh 1.8g PEG to be dissolved in absolute ethyl alcohol, the primary LiFePO4/bis- carbon-coating cladding for being subsequently added preparation is multiple
Condensation material, is configured to the slurry of 5wt%-8wt%, solution is placed in 90 DEG C of baking ovens after stirring at room temperature is dried, and solvent is complete
Full volatilization, subsequent product under nitrogen protection in 500~700 DEG C of 2~3h of high-temperature calcination, take out by cooling, deionized water washing number
After secondary, dry secondary granulation LiFePO4/bis- carbon-coating clad composite material.
Embodiment 3：
1st, the amount concentration ratio for preparing material is 1：1：2 FeSO4·H2O, NH4H2PO4And LiOH, beaker is mixed into equal volume
In, 1.8g citric acids are added under magnetic agitation, add 1.25g mesoporous carbon CMK-3s, ultrasonic agitation 30min to be allowed to uniform after dissolving
Dispersion.
2nd, the dispersed solution of step 1 gained is transferred in reactor, the hydro-thermal reaction 8h at 130 DEG C, reaction
After be cooled to room temperature, product is scrubbed, after forced air drying lithium iron phosphate/carbon doped and compounded material.
3rd, the lithium iron phosphate/carbon doped and compounded material for obtaining step 2 is placed in tube furnace, and under nitrogen protection, 750 DEG C high
Temperature calcining 2h after, cooling take out, with deionized water and absolute ethanol washing for several times after, dry to obtain primary LiFePO4/bis- carbon-coating
Clad composite material.
4th, weigh 2.5g PVP to be dissolved in absolute ethyl alcohol, the primary LiFePO4/bis- carbon-coating cladding for being subsequently added preparation is received
Nano composite material, is configured to the slurry of 3wt%-5wt%, and solution is dried as in 90 DEG C of baking ovens after stirring at room temperature, will be molten
Agent is volatilized completely, and subsequent product under nitrogen protection in 400~600 DEG C of 2~4h of high-temperature calcination, take out by cooling, deionization washing
After washing for several times, dry secondary granulation LiFePO4/bis- carbon-coating clad composite material.
LiFePO4/bis- carbon-coating the clad composite material of the secondary granulation prepared with the embodiment of the present invention 1 is beaten：Will
Binding agent and oil-based solvent are added in double planetary mixer and stir mixing and be uniformly dispersed for 1-2h hours, be subsequently added conductive agent A,
Conductive agent B disperses at a high speed 0.5-1h, and stirring terminates scraper；Major ingredient iron lithium is added toward prefabricated slurry, after mixing, is disperseed at a high speed
2-3h obtains anode sizing agent.Anode sizing agent viscosity when viscosity exceedes the scope, is added appropriate in 4000-10000mPas scopes
In NMP stirrings, regulation to range of viscosities.
The preparation of pole piece and the assembling of battery and test：
LiFePO4/bis- carbon-coating the clad composite material prepared with the embodiment of the present invention 1 as active material, according to it is conventional just
Pole iron lithium technique mashing, negative active core-shell material is MCMB or graphite, and superconduction carbon black uniformly mixes, and deionized water is solvent, CMC
With SBR for binding agent prepares cathode size；Positive and negative electrode slurry is coated, after roll-in, cutting is made positive and negative electrode pole piece；Routinely
Lithium ion battery preparation method, positive and negative electrode is fabricated to lithium ion battery B using winding-structure.
The performance of lithium ion battery is tested, discharge and recharge blanking voltage scope is 2.0~3.6V, determines -20 DEG C low of battery
Warm charge-discharge performance and -20 DEG C of cycle performances.
Table 1 is made by the lithium ion battery A that traditional lithium iron phosphate/carbon covering material is made and the embodiment of the present invention 1
Lithium ion battery B the performance table of comparisons：
Table 1：
| Battery A (tradition) | Battery B (prepared by embodiment 1) | |
| 2.25 | 2.38 | |
| Capacity (Ah) | 5.1 | 5.85 |
| Energy density (Wh/Kg) | 116.6 | 133.7 |
Fig. 1 is the SEM figures of traditional lithium iron phosphate/carbon covering material；Fig. 2 is the phosphoric acid prepared by the embodiment of the present invention 1
The SEM figures of iron lithium/bis- carbon-coating clad composite material；With reference to table 1, Fig. 1 and Fig. 2, the grain of traditional lithium iron phosphate/carbon covering material material
Degree distribution is wider, granularity D50It it is 3.9 μm, specific surface area is 7.59m2/ g, compacted density is 2.25g/cm3, and it is of the invention
After granulation, homogeneity is coated LiFePO4/bis- carbon-coating clad composite material prepared by example 1 than traditional lithium iron phosphate/carbon
Material is good, and primary particle size is small, and specific surface area is big, and material is spherical in shape after granulation, and compacted density is 2.38g/cm3, granularity D50For
5.79 μm, specific surface area is 11.18m2/g；LiFePO4/bis- carbon-coating clad composite material prepared by the embodiment of the present invention 1 is made
The capacity of the battery B of work is 5.85Ah, and energy density is 133.7Wh/Kg, much larger than traditional lithium iron phosphate/carbon covering material institute
The battery A of making.
Fig. 3 be the battery A that is made of traditional lithium iron phosphate/carbon covering material with the embodiment of the present invention 1 be obtained LiFePO4/bis-
- 20 DEG C of charging performance curve maps of the battery B made by carbon-coating clad composite material；As seen from Figure 3, -20 DEG C/0.5C fills
Under the conditions of electricity, the charging constant current ratio of composite battery B is 71.42% obtained by the embodiment of the present invention 1, than traditional positive pole phosphoric acid
Much higher than 51.42% of the charging constant current of iron lithium/carbon encapsulated material battery A, further illustrate the material grain obtained by the present invention
Footpath is small, shortens lithium ion mobility distance, reduces the resistance encountered in transition process, it is possible to decrease the internal resistance of cell, and lifting battery is low
Warm charging performance.
Fig. 4 be the battery A that is made of traditional lithium iron phosphate/carbon covering material with the embodiment of the present invention 1 be obtained LiFePO4/bis-
- 20 DEG C of discharge performance curve maps of the battery B made by carbon-coating clad composite material；As shown in Figure 4, -20 DEG C/1C conditions are transferred
Electricity, the electric discharge ratio of the battery B that the gained composite of the embodiment of the present invention 1 makes is 92.34%, traditional lithium iron phosphate/carbon bag
The electric discharge ratio for covering the battery A of material making is 69.76%, the battery B effects that the gained composite of the embodiment of the present invention 1 makes
Excellent, the composite grain size of the gained of the further comparative illustration embodiment of the present invention 1 is small, shorten lithium ion mobility away from
From surface is in cellular, the specific surface area of material is increased, for lithium ion mobility provides enough passages, double-deck carbon coating
LiFePO4 electric conductivity it is excellent, after granulation, uniform particle sizes, beating process is simple, it is ensured that the homogeneity of slurry and pole piece, changes
The low defect of electronic conductivity, reduces the internal resistance of battery low temperature environment work under kind cryogenic conditions.
Fig. 5 be the battery A that is made of traditional lithium iron phosphate/carbon covering material with the embodiment of the present invention 1 be obtained LiFePO4/bis-
The cycle performance curve map of -20 DEG C of battery B made by carbon-coating clad composite material；It can be seen that -20 DEG C of low temperature
Circulation, the battery B low-temperature circulatings that the gained composite of the embodiment of the present invention 1 makes 200 weeks, capability retention is 88.42%, and
Battery A made by traditional lithium iron phosphate/carbon covering material, low-temperature circulating 200 weeks, capability retention is 67.29%, the present invention
The cycle performance that the gained composite of embodiment 1 prepares battery substantially prepares battery than traditional lithium iron phosphate/carbon covering material
Cycle performance is excellent, and composite prepared by the embodiment of the present invention 1 is using double-deck carbon coating principle, and the material carbon coating of gained is equal
One property increases aggregate particle size than more complete through secondary granulation, is conducive to dispersed in pulping process, electronics under lifting low temperature
Excellent electric conductivity, reduces voltage sluggishness, and particle diameter reduces, it helps lifting low-temperature circulating performance.
The preparation method of LiFePO4/bis- carbon-coating clad composite material that the present invention is provided, by by lithium source, phosphorus source, iron
To HTHP Hydrothermal Synthesiss LiFePO4 is carried out in the three-dimensional nano space of meso-porous carbon material, material exists source presoma " cast "
Grown in mesoporous carbon multidimensional duct, be conducive to controlling the size of material, reduce material primary particle size, increase specific surface area, shortened
Lithium ion mobility distance, for lithium ion mobility provides enough passages, improves the compatibility of material and electrolyte；Using glucose
Deng organic reducing substances as secondary carbon source, can prevent ferrous ion in reaction system be oxidized, through high-temperature calcination after, obtain
To the composite ferric lithium phosphate material of double carbon coating layers, the electronic conductivity of material is improved, improve the low temperature charge-discharge performance of battery
With low-temperature circulating performance；And secondary granulation is carried out to material, increases the aggregate particle size of material, it is to avoid beaten using nanometer technology
Slurry, shorten mashing timeliness, save nanometer beating process used by dispersant, reduce battery make cost of material and technique into
This, increases economic efficiency.
The present invention is not restricted to described in specification and implementation method, therefore for the personnel of familiar field
Additional advantage and modification are easily achieved, therefore in the essence of the universal limited without departing substantially from claim and equivalency range
In the case of god and scope, the present invention is not limited to specific details, representational equipment and shown here as the diagram with description
Example.
Claims (10)
1. the preparation method of a kind of LiFePO4/bis- carbon-coating clad composite material, it is characterised in that：Comprise the following steps：
Step one：Prepare the amount of certain material than source of iron, phosphorus source and lithium source, uniform mixing, add reducing agent simultaneously to dissolve, then add
Enter mesoporous carbon, and carry out ultrasonic agitation, the first mixed liquor is obtained；
Step 2：First mixed liquor obtained in step one is transferred in reactor, hydro-thermal reaction is carried out, room is cooled to after reaction
Temperature, product is scrubbed, the composite of lithium iron phosphate/carbon doping is obtained after forced air drying；
Step 3：The composite of lithium iron phosphate/carbon doping obtained in step 2 is placed in tube furnace, the protection of inert gas
Under, after carrying out first time high-temperature calcination, cooling is taken out, and washing, drying are obtained primary LiFePO4/bis- carbon-coating covered composite yarn material
Material；
Step 4：The additive for taking certain mass is dissolved in absolute ethyl alcohol, and the primary LiFePO4 obtained by addition step 3/bis-
Carbon-coating clad composite material, it is agitated after be configured to the second mixed liquor, by the second mixed liquor be placed in baking oven dry, solvent is complete
Pervaporation, the product of gained carries out second high-temperature calcination under being placed in the protection of inert gas, and cooling, washing and drying are obtained two
The LiFePO4 of secondary granulation/bis- carbon-coating clad composite material.
2. the preparation method of LiFePO4 as claimed in claim 1/bis- carbon-coating clad composite material, it is characterised in that：It is described
The ratio between substance withdrawl syndrome of source of iron, phosphorus source and lithium source in step one is 1：1：3 or 1：1：2.
3. the preparation method of LiFePO4 as claimed in claim 2/bis- carbon-coating clad composite material, it is characterised in that：It is described
Reducing agent in step one is glucose, citric acid, ascorbic acid, one or more of maltose；Phosphorus in the step one
Source is H3PO4、NH4H2PO4In one or more.
4. the preparation method of LiFePO4 as claimed in claim 3/bis- carbon-coating clad composite material, it is characterised in that：It is described
The temperature of hydro-thermal reaction is 120-180 DEG C in step 2, and the hydro-thermal reaction time is 6~12h.
5. the preparation method of LiFePO4 as claimed in claim 4/bis- carbon-coating clad composite material, it is characterised in that：It is described
The temperature of the first time high-temperature calcination in step 3 is 700~800 DEG C, and the time of high-temperature calcination is 2~6h.
6. the preparation method of LiFePO4 as claimed in claim 5/bis- carbon-coating clad composite material, it is characterised in that：It is described
The solid content of the second mixed liquor in step 4 is 3wt%-10wt%.
7. the preparation method of LiFePO4 as claimed in claim 6/bis- carbon-coating clad composite material, it is characterised in that：It is described
The temperature of second high-temperature calcination in step 4 is 400~600 DEG C, and the time of high-temperature calcination is 2~4h.
8. the preparation method of LiFePO4 as claimed in claim 7/bis- carbon-coating clad composite material, it is characterised in that：It is described
Additive in step 4 is one or more in polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone.
9. the preparation method of LiFePO4 as claimed in claim 1/bis- carbon-coating clad composite material, it is characterised in that：Also wrap
Include step 5：Stirring 1-2h is dispersed during binding agent and oil-based solvent are added into double planetary mixer, scraper；Add conductive agent
A and conductive agent B, 0.5-1h is dispersed for stirring, scraper；Add the LiFePO4/bis- carbon of the secondary granulation obtained by step 4
Layer clad composite material, disperses at a high speed 2-3h.
10. the preparation method of LiFePO4 as claimed in claim 9/bis- carbon-coating clad composite material, it is characterised in that：It is described
Binding agent in step 5 is Kynoar binding agent；Described oil-based solvent is 1-METHYLPYRROLIDONE；The conductive agent A
It is conductive black Super-P, conductive agent B is one or more in KS-6, CNT, carbon nano-fiber, Ketjen black.
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