CN110176599A - A kind of graphene In-situ reaction lithium iron phosphate positive material and preparation method thereof - Google Patents
A kind of graphene In-situ reaction lithium iron phosphate positive material and preparation method thereof Download PDFInfo
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- CN110176599A CN110176599A CN201910620098.3A CN201910620098A CN110176599A CN 110176599 A CN110176599 A CN 110176599A CN 201910620098 A CN201910620098 A CN 201910620098A CN 110176599 A CN110176599 A CN 110176599A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- 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
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The present invention discloses a kind of graphene In-situ reaction lithium iron phosphate positive material and preparation method thereof, the method includes using ferrous oxalate cheap and easy to get, ammonium dihydrogen phosphate, lithium carbonate and liquid-state oligomers C3 as raw material, by grinding, spray drying, preheating and calcination processing, graphene In-situ reaction lithium iron phosphate positive material is prepared.By the method for the invention in graphene In-situ reaction lithium iron phosphate positive material obtained, the cladding of graphene efficiently controls the growth of crystal grain, and material internal crystal grain ordered arrangement, accumulation is more closely knit, maintains the structural stability of electrode material；The excellent electric conductivity of graphene accelerates the electron transfer rate of composite material simultaneously, effectively improves the electric conductivity of electrode material.Preparation method provided by the invention is simply easily realized, is environment friendly and pollution-free, low in cost.
Description
Technical field
The present invention relates to technical field of lithium-ion battery more particularly to a kind of graphene In-situ reaction LiFePO4s just
Pole material and preparation method thereof.
Background technique
Due to the growing energy demand of the mankind, exceedingly conventional fossil fuel is relied on and the energy crisis and ring that cause
Border pollution problem is increasingly serious.Therefore, the exploitation of renewable energy be considered as 21st century most worth research project it
One.Renewable energy mainly includes solar energy, wind energy, tide energy etc., however, most of they are with interval, discontinuous
Therefore feature, conveying power grid also face huge security risk.In order to solve this problem, scientist proposes extensive energy storage,
Lower-cost in modularization energy storage is electrochemical energy storage.In numerous variety of energy sources, battery or battery pack are filled as energy storage
It sets, successfully can convert electric energy for chemical energy, there is important application value in life production.Lithium metal is known at present
Most active most light metal, lithium-base battery are shown one's talent in battery large family because of its high-energy density.
Due to olivine-type LiFePO4 (Li Fe PO4) rich because having high open circuit voltage, high theoretical capacity, raw material
Rich, low in cost, safety is reliable, stable circulation, the advantages such as environmentally protective are by it is believed that be most to be commercialized market at present
Change one of the lithium ion power battery cathode material of application potential.However, in practical applications, Li Fe PO4(LFP) as dynamic
Power battery, shows 10-9~10-10S cm-1Low electronic conductivity and 10-14~10-16cm2s-1The lithium ion of difference spreads speed
Rate causes the power battery that the high rate performance gone on business is presented.Currently, Li Fe PO4High rate performance improvement achieves very big grind
Study carefully progress, but still has much room.With the proposition and development of graphene new carbon, more than ten years in past by it is preceding not
Some concerns.Currently, grapheme material, including Li Fe PO4Graphene composite material has been used in LIBs positive electrode.
Effective preparation method is developed to realize Li Fe PO4Combination between graphene discloses different energy storage mechanisms
Synergistic effect mechanism between component is Li Fe PO4With the key of graphene composite material research and the research heat in this field
Point and difficult point.
LiFePO4 (LiFePO4) have specific capacity height, good cycle, stable electrochemical property, it is highly-safe and
Lower-price characteristic becomes new generation of green positive electrode.With the swift and violent hair of the relevant industry such as power battery and energy storage
Exhibition, to LiFePO4The requirement of positive electrode is also higher and higher.And pure phase LiFePO4Conductivity, tap density and ion diffusion
The disadvantages of rate is lower, poorly conductive limits its extensive use.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of graphene In-situ reaction LiFePO4s
Positive electrode and preparation method thereof, it is intended to solve conductivity, tap density and the ion diffusion of existing lithium iron phosphate positive material
The problem that rate is lower, electric conductivity is poor.
Technical scheme is as follows:
A kind of preparation method of graphene In-situ reaction lithium iron phosphate positive material, wherein comprising steps of
A, according to the ratio that Li:Fe:P molar ratio is 1.0-1.5:1-1.5:1 by ferrous oxalate, ammonium dihydrogen phosphate, carbonic acid
Lithium is added in the mixed solvent, and grinding uniformly obtains mixed liquor；
B, it is added a certain amount of homemade liquid-state oligomers C3 in the mixed liquor, it is uniform to continue ground and mixed to it
To positive electrode slurry；
C, spray drying solidifying and setting processing is carried out to the positive electrode slurry, obtains LFP positive electrode material precursor；
D, pre-add heat treatment first is carried out to the positive electrode material precursor under inert atmosphere protection, then carries out crushing thin
Change, finally carries out calcining high-temperature process again, obtain graphene In-situ reaction lithium iron phosphate positive material.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein the mixed solvent is poly-
The mixing of vinylpyrrolidone and/or one of acetylene black and deionized water, ethyl alcohol, isopropanol or acetone or a variety of compositions is molten
Agent.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein the polyvinylpyrrolidine
The relative molecular mass of ketone is 2000-200000.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein the purity of the acetylene black
For 99.0-99.99%.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein the in the mixed solvent is poly-
The quality of vinylpyrrolidone be ferrous oxalate, ammonium dihydrogen phosphate, three kinds of total mass of raw materiales of lithium carbonate 0.5-5%.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein the mixing acetylene black
Quality be ferrous oxalate, ammonium dihydrogen phosphate, three kinds of total mass of raw materiales of lithium carbonate 0.01-3%.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein the liquid-state oligomers C3
Relative molecular mass be 100-100000, the additional amount of the liquid-state oligomers C3 is ferrous oxalate, ammonium dihydrogen phosphate, carbonic acid
The 1-30% of three kinds of total mass of raw materiales of lithium.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein the mixed solvent is poly-
The mixed solvent of one of vinylpyrrolidone and deionized water, ethyl alcohol, isopropanol or acetone or a variety of compositions, additional amount
For ferrous oxalate, ammonium dihydrogen phosphate, 1-100 times of three kinds of total mass of raw materiales of lithium carbonate.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein done by spraying in the step C
Temperature when dry curing process is 110-240 DEG C.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein preheated in the step D
The temperature of processing is 100-400 DEG C, and the processing time is 1-10h.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein crushed in the step D thin
Change processing using processing method be airflow milling crush or ball mill grinding in any one.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein in the step D at calcining
The temperature of reason is 500-900 DEG C, and the processing time is 1-10h.
The preparation method of the graphene In-situ reaction lithium iron phosphate positive material, wherein the inert atmosphere is helium
One of gas, neon, argon gas or nitrogen are a variety of.
A kind of graphene In-situ reaction lithium iron phosphate positive material, wherein using any of the above-described preparation method system
At.
The utility model has the advantages that the present invention is with ferrous oxalate cheap and easy to get, ammonium dihydrogen phosphate, lithium carbonate and liquid-state oligomers C3 work
For raw material, adds surfactant polyethylene pyrrole network alkanone and/or conductive agent acetylene black and pass through grinding, spray drying, preheating
And calcination processing after dispersion and fining, prepare graphene In-situ reaction lithium iron phosphate positive material.It makes by the method for the invention
Graphene In-situ reaction lithium iron phosphate positive material in, the cladding of graphene efficiently controls the growth of crystal grain, in material
Portion's crystal grain ordered arrangement, accumulation is more closely knit, maintains the structural stability of electrode material；The excellent electric conductivity of graphene simultaneously
The electron transfer rate that composite material can be accelerated effectively improves the electric conductivity of electrode material.Preparation method provided by the invention
It is simple easily to realize, is environment friendly and pollution-free, low in cost.
Detailed description of the invention
Fig. 1 is a kind of preparation method preferred embodiment of graphene In-situ reaction lithium iron phosphate positive material of the invention
Flow chart.
Specific embodiment
The present invention provides a kind of graphene In-situ reaction lithium iron phosphate positive materials and preparation method thereof, to make the present invention
Purpose, technical solution and effect it is clearer, clear, the present invention is described in more detail below.It should be appreciated that this place
Specific examples are only used to explain the present invention for description, is not intended to limit the present invention.
Referring to Fig. 1, the preparation method that Fig. 1 is graphene In-situ reaction lithium iron phosphate positive material of the present invention is preferably implemented
The flow chart of example, as shown, including step:
S10, according to the ratio that Li:Fe:P molar ratio is 1.0-1.5:1-1.5:1 by ferrous oxalate, ammonium dihydrogen phosphate, carbon
Sour lithium is added in the mixed solvent, obtains mixed liquor after grinding uniformly；
S20, the liquid-state oligomers C3 that predetermined amount is added in the mixed liquor continue grinding and uniformly obtain positive electrode slurry
Material；
S30, spray drying treatment is carried out to the positive electrode slurry, obtains positive electrode material precursor；
S40, pre-add heat treatment first is carried out to the positive electrode material precursor under an inert atmosphere；To it is described it is advance after obtain
Material carry out dispersion and fining then carry out calcination processing again, obtain graphene In-situ reaction lithium iron phosphate positive material.
In the present embodiment, the ratio for being in step slo first 1.0-1.5:1-1.5:1 according to Li:Fe:P molar ratio
Example weighs ferrous oxalate, ammonium dihydrogen phosphate, lithium carbonate raw material, and the raw material are added in the mixed solvent, the mixing
Solvent be polyvinylpyrrolidone (PVP) and/or one of acetylene black and deionized water, ethyl alcohol, isopropanol or acetone or
The mixed solvent of a variety of compositions；Wherein, the PVP and acetylene black can guarantee during the grinding process as dispersing agent and conductive agent
The ferrous oxalate, ammonium dihydrogen phosphate, lithium carbonate raw material are fully ground uniformly；Preferably, by the raw material and mixing
Solvent is placed on sand mill high speed grinding 1-20h, and uniformly mixed mixed liquor can be obtained.
Further, the relative molecular mass of the polyvinylpyrrolidone is 2000-200000, the in the mixed solvent
The quality of polyvinylpyrrolidone be ferrous oxalate, ammonium dihydrogen phosphate, three kinds of total mass of raw materiales of lithium carbonate 0.05-5%, at this
In range, the raw material after can fully ensure that grinding are evenly dispersed in the mixed solvent.
In the step S20, liquid-state oligomers C3 is added in the mixed liquor, continues to grind 1-10h, obtains anode
Material paste.
Specifically, the amount for the liquid-state oligomers C3 being added in the mixed liquor is iron oxide, phosphoric acid and lithium carbonate three
The relative molecular mass of the 1-30% of kind total mass of raw material, the liquid-state oligomers C3 are 100-100000, the liquid oligomeric
Object C3 is preferably the homopolymer of acrylonitrile or the copolymer of acrylonitrile and other vinyl monomers, and other system's class monomers are poly- second
One of alkene, methyl methacrylate, hydroxyethyl methacrylate, acrylic acid or methylene-succinic acid are a variety of.
In the step S30, spray drying treatment is carried out to the positive electrode slurry, inlet air temperature is adjusted to 110-
240 DEG C, feed rate is set as 25r/min, obtains positive electrode material precursor.
Finally in the step S40, the positive electrode is placed in tubular type retort, under an inert atmosphere to institute
It states positive electrode material precursor and carries out pre-add heat treatment, the temperature of pre-add heat treatment is 100-400 DEG C, and the processing time is 1-10h；It
Crushing calcination processing is carried out to the positive electrode material precursor afterwards, the temperature of calcination processing is 500-900 DEG C, and the processing time is 1-
10h obtains graphene In-situ reaction lithium iron phosphate positive material at this time.Preferably, the inert atmosphere is nitrogen, helium, neon
One of gas, argon gas, Krypton and xenon are a variety of.
Based on the above method, the present invention also provides a kind of graphene In-situ reaction lithium iron phosphate positive materials, wherein uses
The above method is prepared.
Below by specific embodiment the present invention will be further explained explanation:
Embodiment 1
A kind of lithium iron phosphate positive material of graphene In-situ reaction, is prepared via a method which:
(1) Li of corrresponding quality is weighed according to the ratio that Li:Fe:P molar ratio is 1.0-1.5:1-1.5:12CO3
(99.5%), three kinds of ferrous oxalate (99%), ammonium dihydrogen phosphate raw materials；Weighing mass fraction again is above-mentioned substance quality 1%
PVP grinds a few hours in sand mill high speed using deionized water as decentralized medium.
(2) it is Li that quality, which is added,2CO3, ferrous oxalate, three kinds of total mass of raw materiales 15% of ammonium dihydrogen phosphate liquid-state oligomers
C3 continues to grind a few hours, obtains the positive electrode slurry.
(3) slurry that grinding prepares is sprayed, inlet air temperature is adjusted to 150 DEG C, obtains the positive electrode
Presoma powder.
(4) the presoma powder body material for preparing spraying thermal chemical reaction, is put into tubular type retort, under an argon
250 DEG C of preheating 3h, then 900 DEG C of sintering are naturally cooling to room temperature, obtain graphene In-situ reaction ferric phosphate after keeping the temperature 6h
Lithium anode material.
(5) active composite material 0.4g, organic binder (PVDF) 0.05g, second are weighed respectively according to the mass ratio of 8:1:1
Acetylene black 0.05g, after mixing, using N-Methyl pyrrolidone (NMP) as solvent, magnetic agitation 6h, by slurry even spread
On aluminium foil, the dry 4h at 70 DEG C uses sheet-punching machine to be made into the disk of radius 7cm as battery anode slice, by pole piece 110
6h is dried in vacuo at a temperature of DEG C.Using lithium piece as the cathode of lithium ion battery, it is with polypropylene, polyethylene (PP/PE) composite membrane
Diaphragm, with LiPF6/ EC:DEC (volume ratio 1:1) solution is electrolyte, is assembled in anhydrous glove box under an argon
LIR2032 button battery, it is still aging for 24 hours；
(6) electrochemical property test is carried out to assembled battery with Land battery test system.
Embodiment 2
A kind of lithium iron phosphate positive material of graphene In-situ reaction, is prepared via a method which:
(1) Li of corrresponding quality is weighed according to the ratio that Li:Fe:P molar ratio is 1.0-1.5:1-1.5:12CO3
(99.5%), (99%) three kind of ferrous oxalate (99%), ammonium dihydrogen phosphate raw material；Weighing mass fraction again is above-mentioned substance quality
1% PVP grinds a few hours in sand mill high speed using deionized water as decentralized medium.
(2) it is Li that quality, which is added,2CO3, ferrous oxalate, three kinds of total mass of raw materiales of ammonium dihydrogen phosphate 5% liquid-state oligomers
C3 continues to grind a few hours, obtains the positive electrode slurry.
(3) slurry for preparing of grinding be sprayed, inlet air temperature be adjusted to 150 DEG C obtain described in positive electrode before
Drive body powder.
(4) the presoma powder body material for preparing spraying thermal chemical reaction, is put into tubular type retort, under an argon
350 DEG C of preheating 3h, then 600 DEG C of sintering, keep the temperature 6h, after being naturally cooling to room temperature, obtain graphene In-situ reaction ferric phosphate
Lithium anode material.
(5) active composite material 0.4g, organic binder (PVDF) 0.05g, second are weighed respectively according to the mass ratio of 8:1:1
Acetylene black 0.05g, after mixing, using N-Methyl pyrrolidone (NMP) as solvent, magnetic agitation 6h, by slurry even spread
On aluminium foil, the dry 4h at 70 DEG C uses sheet-punching machine to be made into the disk of radius 7cm as battery anode slice, by pole piece 110
6h is dried in vacuo at a temperature of DEG C.Using lithium piece as the cathode of lithium ion battery, it is with polypropylene, polyethylene (PP/PE) composite membrane
Diaphragm, with LiPF6/ EC:DEC (volume ratio 1:1) solution is electrolyte, is assembled in anhydrous glove box under an argon
LIR2032 button battery, it is still aging for 24 hours；
(6) electrochemical property test is carried out to assembled battery with Land battery test system
Embodiment 3
A kind of lithium iron phosphate positive material of graphene In-situ reaction, is prepared via a method which:
(1) Li of corrresponding quality is weighed according to the ratio that Li:Fe:P molar ratio is 1.0-1.5:1-1.5:12CO3
(99.5%), (99%) three kind of ferrous oxalate (99%), ammonium dihydrogen phosphate raw material；Weighing mass fraction again is above-mentioned substance quality
1% PVP, the ethyl alcohol for being 95% using mass fraction grind a few hours as decentralized medium, in sand mill high speed.
(2) it is Li that quality, which is added,2CO3, ferrous oxalate, three kinds of total mass of raw materiales 20% of ammonium dihydrogen phosphate liquid-state oligomers
C3 continues to grind a few hours, obtains the positive electrode slurry.
(3) slurry that grinding prepares is sprayed, inlet air temperature is adjusted to 150 DEG C, obtains the positive electrode
Presoma powder.
(4) the presoma powder body material for preparing spraying thermal chemical reaction, is put into tubular type retort, under an argon
300 DEG C of preheating 1.5h, then 700 DEG C of sintering are naturally cooling to room temperature, obtain graphene In-situ reaction phosphoric acid after keeping the temperature 6h
Iron lithium anode material.
(5) active composite material 0.4g, organic binder (PVDF) 0.05g, second are weighed respectively according to the mass ratio of 8:1:1
Acetylene black 0.05g, after mixing, using N-Methyl pyrrolidone (NMP) as solvent, magnetic agitation 6h, by slurry even spread
On aluminium foil, the dry 4h at 70 DEG C uses sheet-punching machine to be made into the disk of radius 7cm as battery anode slice, by pole piece 110
6h is dried in vacuo at a temperature of DEG C.Using lithium piece as the cathode of lithium ion battery, it is with polypropylene, polyethylene (PP/PE) composite membrane
Diaphragm, with LiPF6/ EC:DEC (volume ratio 1:1) solution is electrolyte, is assembled in anhydrous glove box under an argon
LIR2032 button battery, it is still aging for 24 hours；
(6) electrochemical property test is carried out to assembled battery with Land battery test system.
Embodiment 4
A kind of lithium iron phosphate positive material of graphene In-situ reaction, is prepared via a method which:
(1) Li of corrresponding quality is weighed according to the ratio of Li:Fe:P molar ratio 1.0-1.5:1-1.5:12CO3(99.5%),
(99%) three kind of ferrous oxalate (99%), ammonium dihydrogen phosphate raw material；Weighing mass fraction again is above-mentioned substance quality 0.5%
PVP grinds a few hours in sand mill high speed using deionized water as decentralized medium.
(2) it is Li that quality, which is added,2CO3, ferrous oxalate, three kinds of total mass of raw materiales 20% of ammonium dihydrogen phosphate liquid-state oligomers
C3 continues to grind a few hours, obtains the positive electrode slurry.
(3) slurry that grinding prepares is sprayed, inlet air temperature is adjusted to 150 DEG C, and feed rate is set as 25r/
min.Obtain the positive electrode material precursor powder.
(4) the presoma powder body material for preparing spraying thermal chemical reaction, is put into tubular type retort, under an argon
700 DEG C of sintering are naturally cooling to room temperature, obtain graphene In-situ reaction lithium iron phosphate positive material after keeping the temperature 6h.
(5) active composite material 0.4g, organic binder (PVDF) 0.05g, second are weighed respectively according to the mass ratio of 8:1:1
Acetylene black 0.05g, after mixing, using N-Methyl pyrrolidone (NMP) as solvent, magnetic agitation 6h, by slurry even spread
On aluminium foil, the dry 4h at 70 DEG C uses sheet-punching machine to be made into the disk of radius 7cm as battery anode slice, by pole piece 110
6h is dried in vacuo at a temperature of DEG C.Using lithium piece as the cathode of lithium ion battery, it is with polypropylene, polyethylene (PP/PE) composite membrane
Diaphragm, with LiPF6/ EC:DEC (volume ratio 1:1) solution is electrolyte, is assembled in anhydrous glove box under an argon
LIR2032 button battery, it is still aging for 24 hours；
(6) electrochemical property test is carried out to assembled battery with Land battery test system.
Embodiment 5
A kind of lithium iron phosphate positive material of graphene In-situ reaction, is prepared via a method which:
(1) Li of corrresponding quality is weighed according to the ratio of Li:Fe:P molar ratio 1.0-1.5:1-1.5:12CO3(99.5%),
(99%) three kind of ferrous oxalate (99%), ammonium dihydrogen phosphate raw material；The PVP that mass fraction is above-mentioned substance quality 2% is weighed again,
Using deionized water as decentralized medium, a few hours are ground in sand mill high speed.
(2) it is Li that quality, which is added,2CO3, ferrous oxalate, three kinds of total mass of raw materiales 5% of ammonium dihydrogen phosphate liquid-state oligomers
C3 continues to grind a few hours, obtains the positive electrode slurry.
(3) slurry that grinding prepares is sprayed, inlet air temperature is adjusted to 150 DEG C, and feed rate is set as 25r/
min.Obtain the positive electrode material precursor powder.
(4) the presoma powder body material for preparing spraying thermal chemical reaction, is put into tubular type retort, under nitrogen atmosphere
700 DEG C of sintering are naturally cooling to room temperature, obtain graphene In-situ reaction lithium iron phosphate positive material after keeping the temperature 6h.
(5) active composite material 0.4g, organic binder (PVDF) 0.05g, second are weighed respectively according to the mass ratio of 8:1:1
Acetylene black 0.05g, after mixing, using N-Methyl pyrrolidone (NMP) as solvent, magnetic agitation 6h, by slurry even spread
On aluminium foil, the dry 4h at 70 DEG C uses sheet-punching machine to be made into the disk of radius 7cm as battery anode slice, by pole piece 110
6h is dried in vacuo at a temperature of DEG C.Using lithium piece as the cathode of lithium ion battery, it is with polypropylene, polyethylene (PP/PE) composite membrane
Diaphragm, with LiPF6/ EC:DEC (volume ratio 1:1) solution is electrolyte, is assembled in anhydrous glove box under an argon
LIR2032 button battery, it is still aging for 24 hours；
(6) electrochemical property test is carried out to assembled battery with Land battery test system.
Embodiment 6
A kind of lithium iron phosphate positive material of graphene In-situ reaction, is prepared via a method which:
(1) Li of corrresponding quality is weighed according to the ratio of Li:Fe:P molar ratio 1.0-1.5:1-1.5:12CO3(99.5%),
(99%) three kind of ferrous oxalate (99%), ammonium dihydrogen phosphate raw material；Weighing mass fraction again is above-mentioned substance quality 0.01%
Acetylene black grinds a few hours in sand mill high speed using deionized water as decentralized medium.
(2) it is Li that quality, which is added,2CO3, ferrous oxalate, three kinds of total mass of raw materiales 20% of ammonium dihydrogen phosphate liquid-state oligomers
C3 continues to grind a few hours, obtains the positive electrode slurry.
(3) slurry that grinding prepares is sprayed, inlet air temperature is adjusted to 150 DEG C, and feed rate is set as 25r/
min.Obtain the positive electrode material precursor powder.
(4) the presoma powder body material for preparing spraying thermal chemical reaction, is put into tubular type retort, under an argon
250 DEG C of preheating 2h are down to room temperature and crush again, and then 900 DEG C of sintering are naturally cooling to room temperature, obtain graphene after keeping the temperature 6h
In-situ reaction lithium iron phosphate positive material.
(5) active composite material 0.4g, organic binder (PVDF) 0.05g, second are weighed respectively according to the mass ratio of 8:1:1
Acetylene black 0.05g, after mixing, using N-Methyl pyrrolidone (NMP) as solvent, magnetic agitation 6h, by slurry even spread
On aluminium foil, the dry 4h at 70 DEG C uses sheet-punching machine to be made into the disk of radius 7cm as battery anode slice, by pole piece 110
6h is dried in vacuo at a temperature of DEG C.Using lithium piece as the cathode of lithium ion battery, it is with polypropylene, polyethylene (PP/PE) composite membrane
Diaphragm, with LiPF6/ EC:DEC (volume ratio 1:1) solution is electrolyte, is assembled in anhydrous glove box under an argon
LIR2032 button battery, it is still aging for 24 hours；
(6) electrochemical property test is carried out to assembled battery with Land battery test system.
Embodiment 7
A kind of lithium iron phosphate positive material of graphene In-situ reaction, is prepared via a method which:
(1) Li of corrresponding quality is weighed according to the ratio of Li:Fe:P molar ratio 1.0-1.5:1-1.5:12CO3(99.5%),
(99%) three kind of ferrous oxalate (99%), ammonium dihydrogen phosphate raw material；The second that mass fraction is above-mentioned substance quality 0.8% is weighed again
Acetylene black grinds a few hours in sand mill high speed using deionized water as decentralized medium.
(2) it is Li that quality, which is added,2CO3, ferrous oxalate, three kinds of total mass of raw materiales 20% of ammonium dihydrogen phosphate liquid-state oligomers
C3 continues to grind a few hours, obtains the positive electrode slurry.
(3) slurry that grinding prepares is sprayed, inlet air temperature is adjusted to 160 DEG C, and feed rate is set as 25r/
min.Obtain the positive electrode material precursor powder.
(4) the presoma powder body material for preparing spraying thermal chemical reaction, is put into tubular type retort, under an argon
300 DEG C of preheating 2h are down to room temperature and crush again, and then 850 DEG C of sintering are naturally cooling to room temperature, obtain graphene after keeping the temperature 6h
In-situ reaction lithium iron phosphate positive material.
(5) active composite material 0.4g, organic binder (PVDF) 0.05g, second are weighed respectively according to the mass ratio of 8:1:1
Acetylene black 0.05g, after mixing, using N-Methyl pyrrolidone (NMP) as solvent, magnetic agitation 6h, by slurry even spread
On aluminium foil, the dry 4h at 70 DEG C uses sheet-punching machine to be made into the disk of radius 7cm as battery anode slice, by pole piece 110
6h is dried in vacuo at a temperature of DEG C.Using lithium piece as the cathode of lithium ion battery, it is with polypropylene, polyethylene (PP/PE) composite membrane
Diaphragm, with LiPF6/ EC:DEC (volume ratio 1:1) solution is electrolyte, is assembled in anhydrous glove box under an argon
LIR2032 button battery, it is still aging for 24 hours；
(6) electrochemical property test is carried out to assembled battery with Land battery test system.
Embodiment 8
A kind of lithium iron phosphate positive material of graphene In-situ reaction, is prepared via a method which:
(1) Li of corrresponding quality is weighed according to the ratio of Li:Fe:P molar ratio 1.0-1.5:1-1.5:12CO3(99.5%),
(99%) three kind of ferrous oxalate (99%), ammonium dihydrogen phosphate raw material；The second that mass fraction is above-mentioned substance quality 3.0% is weighed again
Acetylene black grinds a few hours in sand mill high speed using deionized water as decentralized medium.
(2) it is Li that quality, which is added,2CO3, ferrous oxalate, three kinds of total mass of raw materiales 10% of ammonium dihydrogen phosphate liquid-state oligomers
C3 continues to grind a few hours, obtains the positive electrode slurry.
(3) slurry that grinding prepares is sprayed, inlet air temperature is adjusted to 150 DEG C, and feed rate is set as 25r/
min.Obtain the positive electrode material precursor powder.
(4) the presoma powder body material for preparing spraying thermal chemical reaction, is put into tubular type retort, under an argon
400 DEG C of preheating 2h are down to room temperature and crush again, and then 550 DEG C of sintering are naturally cooling to room temperature, obtain graphene after keeping the temperature 6h
In-situ reaction lithium iron phosphate positive material.
(5) active composite material 0.4g, organic binder (PVDF) 0.05g, second are weighed respectively according to the mass ratio of 8:1:1
Acetylene black 0.05g, after mixing, using N-Methyl pyrrolidone (NMP) as solvent, magnetic agitation 6h, by slurry even spread
On aluminium foil, the dry 4h at 70 DEG C uses sheet-punching machine to be made into the disk of radius 7cm as battery anode slice, by pole piece 110
6h is dried in vacuo at a temperature of DEG C.Using lithium piece as the cathode of lithium ion battery, it is with polypropylene, polyethylene (PP/PE) composite membrane
Diaphragm, with LiPF6/ EC:DEC (volume ratio 1:1) solution is electrolyte, is assembled in anhydrous glove box under an argon
LIR2032 button battery, it is still aging for 24 hours；
(6) electrochemical property test is carried out to assembled battery with Land battery test system.
Embodiment 9
A kind of lithium iron phosphate positive material of graphene In-situ reaction, is prepared via a method which:
(1) Li of corrresponding quality is weighed according to the ratio of Li:Fe:P molar ratio 1.0-1.5:1-1.5:12CO3(99.5%),
(99%) three kind of ferrous oxalate (99%), ammonium dihydrogen phosphate raw material；The second that mass fraction is above-mentioned substance quality 1.5% is weighed again
Acetylene black grinds a few hours in sand mill high speed to go ethyl alcohol as decentralized medium.
(2) it is Li that quality, which is added,2CO3, ferrous oxalate, three kinds of total mass of raw materiales 10% of ammonium dihydrogen phosphate liquid-state oligomers
C3 continues to grind a few hours, obtains the positive electrode slurry.
(3) slurry that grinding prepares is sprayed, inlet air temperature is adjusted to 150 DEG C, and feed rate is set as 25r/
min.Obtain the positive electrode material precursor powder.
(4) the presoma powder body material for preparing spraying thermal chemical reaction, is put into tubular type retort, under an argon
100 DEG C of preheating 2h are down to room temperature and crush again, and then 900 DEG C of sintering are naturally cooling to room temperature, obtain graphene after keeping the temperature 6h
In-situ reaction lithium iron phosphate positive material.
(5) active composite material 0.4g, organic binder (PVDF) 0.05g, second are weighed respectively according to the mass ratio of 8:1:1
Acetylene black 0.05g, after mixing, using N-Methyl pyrrolidone (NMP) as solvent, magnetic agitation 6h, by slurry even spread
On aluminium foil, the dry 4h at 70 DEG C uses sheet-punching machine to be made into the disk of radius 7cm as battery anode slice, by pole piece 110
6h is dried in vacuo at a temperature of DEG C.Using lithium piece as the cathode of lithium ion battery, it is with polypropylene, polyethylene (PP/PE) composite membrane
Diaphragm, with LiPF6/ EC:DEC (volume ratio 1:1) solution is electrolyte, is assembled in anhydrous glove box under an argon
LIR2032 button battery, it is still aging for 24 hours；
(6) electrochemical property test is carried out to assembled battery with Land battery test system.
Embodiment 10
A kind of lithium iron phosphate positive material of graphene In-situ reaction, is prepared via a method which:
(1) Li of corrresponding quality is weighed according to the ratio of Li:Fe:P molar ratio 1.0-1.5:1-1.5:12CO3(99.5%),
(99%) three kind of ferrous oxalate (99%), ammonium dihydrogen phosphate raw material；The second that mass fraction is above-mentioned substance quality 1.5% is weighed again
Acetylene black and 2.0%PVP grind a few hours in sand mill high speed to go deionized water as decentralized medium.
(2) it is Li that quality, which is added,2CO3, ferrous oxalate, three kinds of total mass of raw materiales 20% of ammonium dihydrogen phosphate liquid-state oligomers
C3 continues to grind a few hours, obtains the positive electrode slurry.
(3) slurry that grinding prepares is sprayed, inlet air temperature is adjusted to 150 DEG C, and feed rate is set as 25r/
min.Obtain the positive electrode material precursor powder.
(4) the presoma powder body material for preparing spraying thermal chemical reaction, is put into tubular type retort, under an argon
300 DEG C of preheating 2h are down to room temperature and crush again, and then 900 DEG C of sintering are naturally cooling to room temperature, obtain graphene after keeping the temperature 6h
In-situ reaction lithium iron phosphate positive material.
(5) active composite material 0.4g, organic binder (PVDF) 0.05g, second are weighed respectively according to the mass ratio of 8:1:1
Acetylene black 0.05g, after mixing, using N-Methyl pyrrolidone (NMP) as solvent, magnetic agitation 6h, by slurry even spread
On aluminium foil, the dry 4h at 70 DEG C uses sheet-punching machine to be made into the disk of radius 7cm as battery anode slice, by pole piece 110
6h is dried in vacuo at a temperature of DEG C.Using lithium piece as the cathode of lithium ion battery, it is with polypropylene, polyethylene (PP/PE) composite membrane
Diaphragm, with LiPF6/ EC:DEC (volume ratio 1:1) solution is electrolyte, is assembled in anhydrous glove box under an argon
LIR2032 button battery, it is still aging for 24 hours；
(6) electrochemical property test is carried out to assembled battery with Land battery test system.
In conclusion the present invention is with ferrous oxalate cheap and easy to get, ammonium dihydrogen phosphate, lithium carbonate and liquid-state oligomers C3 work
For raw material, polyethylene pyrrole network alkanone and acetylene black is added as additive, by grinding, spray drying, preheating, crushing and
Calcination processing prepares graphene In-situ reaction lithium iron phosphate positive material.Graphene obtained is in situ by the method for the invention
In composite lithium iron phosphate cathode material, the cladding of graphene efficiently controls the growth of crystal grain, material internal crystal grain ordered arrangement,
Accumulation is more closely knit, maintains the structural stability of electrode material；The excellent electric conductivity of graphene accelerates composite wood simultaneously
The electron transfer rate of material effectively improves the electric conductivity of electrode material.Preparation method provided by the invention is simply easily realized, is environmentally friendly
It is pollution-free, low in cost.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of graphene In-situ reaction lithium iron phosphate positive material, which is characterized in that comprising steps of
A, according to the ratio that Li:Fe:P molar ratio is 1.0-1.5:1-1.5:1 by Li2CO3, ferrous oxalate, ammonium dihydrogen phosphate be added
To in the mixed solvent, grinding uniformly obtains mixed liquor；
B, the liquid-state oligomers C3 of predetermined amount is added in the mixed liquor, continues grinding and uniformly obtains positive electrode slurry；
C, spray drying treatment is carried out to the positive electrode slurry, obtains positive electrode material precursor；
D, pre-add heat treatment first is carried out to the positive electrode material precursor under an inert atmosphere, then carries out calcination processing again, obtains
To graphene In-situ reaction lithium iron phosphate positive material.
2. the preparation method of graphene In-situ reaction lithium iron phosphate positive material according to claim 1, which is characterized in that
The mixed solvent be polyvinylpyrrolidone and/or one of acetylene black and deionized water, ethyl alcohol, isopropanol or acetone or
The mixed solvent of a variety of compositions.
3. the preparation method of graphene In-situ reaction lithium iron phosphate positive material according to claim 2, which is characterized in that
The relative molecular mass of the polyvinylpyrrolidone is 2000-200000.
4. the preparation method of graphene In-situ reaction lithium iron phosphate positive material according to claim 2, which is characterized in that
The quality of the in the mixed solvent polyvinylpyrrolidone is ferrous oxalate, three kinds of ammonium dihydrogen phosphate, lithium carbonate total mass of raw materiales
0.5-5%.
5. the preparation method of graphene In-situ reaction lithium iron phosphate positive material according to claim 1, which is characterized in that
The relative molecular mass of the liquid-state oligomers C3 is 100-100000, and the additional amount of the liquid-state oligomers C3 is that oxalic acid is sub-
Iron, ammonium dihydrogen phosphate, three kinds of total mass of raw materiales of lithium carbonate 10-30%.
6. the preparation method of graphene In-situ reaction lithium iron phosphate positive material according to claim 1, which is characterized in that
Temperature in the step C when spray drying treatment is 110-240 DEG C.
7. the preparation method of graphene In-situ reaction lithium iron phosphate positive material according to claim 1, which is characterized in that
The temperature that pre-add is heat-treated in the step D is 100-400 DEG C, and the processing time is 1-10h, the use of the dispersion and fining processing
Processing method be airflow milling crush or ball mill grinding in any one, the temperature of the calcination processing is 500-900 DEG C, place
The reason time is 1-10h.
8. the preparation method of graphene In-situ reaction lithium iron phosphate positive material according to claim 1, which is characterized in that
The mixed solvent is one of polyvinylpyrrolidone and deionized water, ethyl alcohol, isopropanol or acetone or a variety of compositions
Mixed solvent, additional amount are ferrous oxalate, ammonium dihydrogen phosphate, 1-100 times of three kinds of total mass of raw materiales of lithium carbonate.
9. the preparation method of graphene In-situ reaction lithium iron phosphate positive material according to claim 1, which is characterized in that
The inert atmosphere is one of helium, neon, argon gas or nitrogen or a variety of.
10. a kind of graphene In-situ reaction lithium iron phosphate positive material, which is characterized in that using such as any institute of claim 1-9
The preparation method stated is made.
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