CN107394152A - The spherical composite of the high graphene-based LiFePO4 of conductance, its preparation method and include its lithium ion battery - Google Patents

The spherical composite of the high graphene-based LiFePO4 of conductance, its preparation method and include its lithium ion battery Download PDF

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CN107394152A
CN107394152A CN201710579932.XA CN201710579932A CN107394152A CN 107394152 A CN107394152 A CN 107394152A CN 201710579932 A CN201710579932 A CN 201710579932A CN 107394152 A CN107394152 A CN 107394152A
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graphene
lithium
composite
spherical
ferric
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CN107394152B (en
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王张健
杨顺毅
吴小珍
崔伟超
黄友元
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Jiangsu Beiteri Nano Technology Co ltd
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Shenzhen Battery Nanotechnology Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of spherical composite of high graphene-based LiFePO4 of conductance, its preparation method and lithium ion battery comprising this composite.The present invention passes through series techniques such as " graphene mix spheroidization CVD growth in situ graphene with LFP precursor molecule levels ", prepare the spherical composite of the graphene-based LiFePO4 of high conductance, the graphene of two states is included in the composite, it is a kind of to be introduced in presoma mix stages；Another growth in situ specifically, the composite includes the secondary spherical particle being made up of primary particle, and is grown in the graphene of the secondary spherical particle surface on the surface of material；Wherein, primary particle is the lithium iron phosphate particles comprising graphene.Lithium ion battery is prepared as positive electrode active materials using the graphene composite material of the present invention, can add or save additional conductive agent, obtained lithium ion battery can take into account the performances such as material gram volume, low temperature, multiplying power and processing, circulation well.

Description

The spherical composite of the high graphene-based LiFePO4 of conductance, its preparation method and comprising Its lithium ion battery
Technical field
The invention belongs to field of lithium ion battery anode, in particular it relates to which a kind of high conductance is graphene-based The spherical composite of LiFePO4, its preparation method and the lithium ion battery comprising this composite.
Background technology
Existing olivine-type LiFePO4(LFP) anode material for lithium-ion batteries is used as, has theoretical capacity higher The advantages that (170mAh/g), good cycle, Stability Analysis of Structures, environment-friendly, aboundresources, had an optimistic view of extensively；However, due to LiFePO4Itself there is relatively low electron conductivity and lithium ion diffusion rate, significantly limit LiFePO4Chemical property Performance, and hinder LiFePO4Extensive use of the positive electrode on power, start and stop power supply.
By to LiFePO4Found after carrying out numerous studies, control the scale topography of particle, Surface coating and metal ion Doping can be effectively improved LiFePO4Chemical property, wherein preparing the little particle LiFePO of regular shape4Can effectively it contract Short Li+Migration distance inside it, and then improve LiFePO4The performances such as the low temperature of material, multiplying power.Patent CN 102623701 A discloses a kind of preparation method of low-temperature nanometer lithium iron phosphate cathode material, passes through " wet method fine grinding-spray drying-pre- Broken-low-temperature sintering of burning-Ultrafine Grinding-spray drying-gas-secondary high-temperature sintering " technology, it is 60- that primary particle, which is made, 70nm LiFePO 4 material, its low temperature performance excellent, but its tap density is not high, and processing, high temperature and cycle performance be not good enough, together When because process it is oversize so that energy consumption is big, uneconomical environmental protection.
To improve LiFePO4 tap density, it is a general orientation to prepare spherical LiFePO 4.Prepare ball shape ferric phosphate at present The method of lithium is mainly liquid phase method, and this method complex operation, cost are higher, are unfavorable for industrialized production.Patent CN 102642820 A disclose a kind of preparation method of high-density spherical ferric lithium phosphate, by the way that " ball mill wet mixing-spray drying-is pre- Burning-wet-milling-spray drying-roasting " technology, obtained ball shape ferric phosphate lithium material tap density is high, and slurry fluidity is good, But whole process is oversize, and homogeneity of product is difficult to control, and cost is high, uneconomical.The A of patent CN 103996846 disclose one kind The preparation method of the controllable lithium iron phosphate positive material of granularity, pass through " fluid spray of Ultrafine Grinding-two-high temperature sintering " technique skill Art, the ball shape ferric phosphate lithium material that aggregate particle size is 1-10um is made, its gram volume is high, good rate capability, but its spheroid is not close Real, tap density is not high.
Material with carbon-coated surface is one of now more commonly used method of raising LiFePO 4 material chemical property.It is current normal Carbon coating structure obtained by synthetic method is mainly based on amorphous carbon.There are some researches show Li+Ion is in sp2Structure Carbon in ratio in sp3It is easier to spread in the carbon of structure or impalpable structure；And sp2The carbon electrical conductivity of hydridization is more than sp3Hydridization With the electrical conductivity of disordered carbon.Carbon in graphene is completely with sp2Form is present, therefore LiFePO4 and the compound of graphene are to carry The lithium ion diffusion rate and electronic conductivity effective means of high LiFePO 4 material.The A of patent CN 105742629 disclose one The in-situ preparation method of kind lithium ion battery anode material lithium iron phosphate/graphene complex, passes through " graphene oxide conduction liquid Mix-dry-sintering with LFP precursor molecule levels " technology, obtained LiFePO4/graphene complex electric conductivity compared with Good, low temperature, high rate performance are pretty good, but processing characteristics is not good enough.The A of patent CN 104934608 disclose a kind of graphene bag in situ The preparation method of anode material for lithium-ion batteries is covered, it is equal in LFP material powder surface in situ coated graphite alkene, graphene growth Even property is not good enough, lifts LFP chemical property unobvious.
Thus, it is necessary to research and develop a kind of phosphoric acid that can take into account the properties such as high power capacity, low temperature, multiplying power and processing, circulation The spherical composite of iron lithium.
The content of the invention
In view of the shortcomings of the prior art, an object of the present invention is to provide a kind of graphene-based LiFePO4 of high conductance Spherical composite, its preparation method and the lithium ion battery comprising this composite.Using the graphene-based phosphoric acid of the present invention The spherical composite of iron lithium prepares lithium ion battery as positive electrode active materials, can add or save additional conductive agent, obtain Lithium ion battery can take into account the performances such as material gram volume, low temperature, multiplying power and processing, circulation well.
In a first aspect, the present invention provides a kind of graphene-based spherical composite of LiFePO4, the composite includes The secondary spherical particle being made up of primary particle, and the graphene of the secondary spherical particle surface is grown in, wherein, it is described The lithium iron phosphate particles of graphene are included in primary particle.
In the present invention, " graphene for being grown in the secondary spherical particle surface " is preferably that CVD growth in situ exists The graphene of secondary spherical particle surface.
Preferably, the particle diameter of the primary particle is 20-300nm, for example, 20nm, 30nm, 40nm, 50nm, 60nm, 80nm、100nm、110nm、125nm、140nm、150nm、165nm、180nm、200nm、220nm、240nm、260nm、275nm、 285nm or 300nm etc..
Preferably, the median of the secondary spherical particle is 3-9 μm, such as 3 μm, 4 μm, 5 μm, 6 μm, 6.5 μm, 7 μ M, 7.5 μm, 8 μm or 9 μm etc..
Preferably, the graphene included in the primary particle accounts for the 1-5wt.% of composite gross mass, such as 1wt.%, 2wt.%, 2.5wt.%, 3wt.%, 3.5wt.%, 4wt.%, 4.5wt.% or 5wt.% etc., preferably 1- 2wt.%.
Preferably, the number of plies of the graphene of the secondary spherical particle surface is grown in for individual layer or less than 10 layers.
Preferably, the secondary median of the composite be 3-9 μm, such as 3 μm, 4 μm, 4.5 μm, 5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm or 9 μm etc..
Preferably, the powder conductivity rate of the composite is in more than 1S/cm, such as 1S/cm, 3S/cm, 5S/cm, 7S/ Cm, 10S/cm or 12S/cm etc..
Second aspect, the present invention provide the preparation method of composite as described in relation to the first aspect, methods described include with Lower step：
(1) the ferric lithium phosphate precursor slurry for including graphene is prepared；
(2) it is spray-dried, obtains the secondary spherical ferric lithium phosphate precursor being made up of primary particle；
(3) secondary spherical ferric lithium phosphate precursor is placed in reacting furnace, is warming up to 600-750 DEG C, in protective atmosphere Under be passed through organic compound, carry out growth in situ graphene, obtain the spherical composite of graphene-based LiFePO4.
In the present invention, step (3) is described to be warming up to 600-750 DEG C, for example, 600 DEG C, 620 DEG C, 630 DEG C, 640 DEG C, 650 DEG C, 665 DEG C, 680 DEG C, 700 DEG C, 710 DEG C, 720 DEG C, 730 DEG C, 740 DEG C or 750 DEG C etc..
In the method for the present invention, mixed, solved existing with LiFePO4 LFP precursor molecule levels by adding graphene In technology using conventional carbon source prepare carbon content during nano-level sphere LFP it is low when poorly conductive, and spheroid when carbon content is high The problem of boring is more, tap density is not high.
In the method for the present invention, graphene CVD growth in situ is in LFP during spherical lithium iron phosphate precursor sinters Spherome surface, the reunion of primary particle but also electric conductivity was improved when not only having inhibited the LFP to sinter, its powder conductivity rate is up to 1S/cm More than, improve more than 100 times, conductive agent can not be added in its battery applications, this be advantageous to further to improve it is with slurry contain admittedly, pass through Ji environmental protection.Moreover, in LFP battery applications, LFP spherome surfaces coat a layer graphene, inhibit LFP and electrolyte well Side reaction, it will be apparent that improve its high temperature storage and high temperature cyclic performance.
LFP powder is prepared with the first sintering of routine, is then compared again in the technique of surface in situ growth graphene, this The method of invention grows graphene in sintering process, have growth evenly, the advantages of process is simpler, effect is more preferable.
The more closely knit and good conductivity using the composite LiFePO4 internal particle that is prepared of method of the present invention, this Be advantageous to preferably improve nanoscale LFP processing characteristicies, reduce LFP internal resistances, improve its multiplying power, cryogenic property.
Preferably, step (1) the ferric lithium phosphate precursor slurry comprising graphene is dispersed slurry.
As the optimal technical scheme of the method for the invention, step (1) the LiFePO4 forerunner for including graphene Somaplasm material is prepared via a method which to obtain：
(A) lithium source, ferric phosphate, optional dopant and optional carbon source are subjected to dispensing, obtain compound；
(B) compound is mixed with graphene, optional dispersant and deionized water, grinding distribution, obtains including stone The ferric lithium phosphate precursor slurry of black alkene.
Preferably, step (A) lithium source, ferric phosphate and optional dopant are according to mol ratio Li:Fe:P:M=(1.0- 1.1):1:(1-1.05):(0-2.0%) carries out dispensing, wherein, M is the doped chemical in dopant.
Preferably, step (A) described lithium source include monohydrate lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium oxalate or Any a kind or at least two kinds of of combination in lithium fluoride, but be not limited to the above-mentioned lithium source enumerated, other it is commonly used in the art can The lithium source for reaching same effect can also be used for the present invention.
Preferably, step (A) described dopant be Mg, Mn, Ti, V, Nb, Ni or Co compound in any a kind or at least 2 kinds of combination.
Preferably, in step (A), using the gross mass of lithium source, ferric phosphate, optional dopant and optional carbon source as 100wt.% is counted, and the percentage that the carbon source accounts for gross mass is 0wt.%-1.5wt.%, such as 0wt.%, 0.2wt.%, 0.5wt.%, 0.7wt.%, 1.0wt.%, 1.2wt.%, 1.3wt.%, 1.4wt.% or 1.5wt.% etc..Wherein, percentage Represented for 0wt.% and be added without carbon source.
In the present invention, " carbon source accounts for the percentage of gross mass " is carbon content.
In the present invention, " optional carbon source " refers to：Carbon source can be added, carbon source can also be added without.
Preferably, step (A) described carbon source includes ascorbic acid, cellulose, polypropylene, epoxy resin, sucrose, grape 1 kind or at least two kinds of of combination in sugar, fructose, citric acid, polyethylene glycol, starch, phenolic resin, but it is not limited to above-mentioned row The carbon source of act, other carbon sources that can reach same effect commonly used in the art can also be used for the present invention.
In the present invention, " optional dopant " refers to：Dopant can be added, dopant can also be added without.
Preferably, in step (B), the percentage that graphene accounts for mixture quality is 0.1-1.5wt.%, such as 0.1wt.%, 0.5wt.%, 0.7wt.%, 0.8wt.%, 1wt.%, 1.2wt.%, 1.3wt.%, 1.4wt.% or 1.5wt.% etc..
Preferably, in step (B), percentage that dispersant accounts for mixture quality is 0-2wt.%, such as 0wt.%, 0.5wt.%, 0.7wt.%, 1.0wt.%, 1.2wt.%, 1.4wt.%, 1.5wt.%, 1.6wt.%, 1.8wt.% or 2.0wt.% etc..Wherein, percentage is that 0wt.% representatives are added without dispersant.
In the present invention, " optional dispersant " refers to：Dispersant can be added, dispersant can also be added without.
Preferably, in step (B), the quality of deionized water is 1-6 times of mixture quality, for example, 1 times, 1.2 times, 1.5 Again, 2 times, 2.5 times, 3 times, 4 times, 4.5 times, 5 times, 5.5 times or 6 times etc..
Preferably, step (B) described graphene includes graphene powder, graphene conductive liquid, graphene oxide conduction liquid In any a kind or at least two kinds of of combination, but be not limited to the above-mentioned graphene enumerated, other are commonly used in the art to can reach The graphene of same effect can also be used for the present invention.
Preferably, it is preferable that step (B) described dispersant is glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone Or any a kind or at least two kinds of of combination in polyvinyl alcohol.
Preferably, the time of step (B) described grinding distribution is 2-20h, for example, 2h, 4h, 5h, 8h, 10h, 12h, 15h, 16h, 18h or 20h etc..
As the optimal technical scheme of the method for the invention, step (2) spray drying is two fluids, pneumoelectric combines Any a kind in the fluid of formula two, four fluid sprays.
Preferably, when step (2) carries out the spray drying, the inlet temperature of spray dryer is 200-350 DEG C, such as 200 DEG C, 210 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 255 DEG C, 270 DEG C, 280 DEG C, 290 DEG C, 300 DEG C, 320 DEG C, 330 DEG C or 350 DEG C etc., outlet temperature is not less than 70 DEG C.
Preferably, step (3) described reacting furnace is rotary furnace, and rotary furnace is with 1-10r/min rotational speed, rotating speed example Such as 1r/min, 2r/min, 3r/min, 5r/min, 6r/min, 7r/min, 8r/min, 8.5r/min, 9r/min and 10r/min Deng.
Preferably, the heating rate of step (3) described reacting furnace is 1-10 DEG C/min, for example, 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 7 DEG C/min, 8 DEG C/min or 10 DEG C/min etc..
Preferably, step (3) described protective atmosphere is any a kind in argon gas atmosphere, nitrogen atmosphere or hydrogen atmosphere Or at least two kinds of combination atmosphere.
Preferably, step (3) described organic compound is included in methane, ethane, ethene, acetylene, acetone, benzene and toluene Any a kind or at least two kinds of of combination, but be not limited to the above-mentioned organic compound enumerated, other are commonly used in the art to can reach The organic compound of same effect can also be used for the present invention.
Preferably, step (3) flow velocity for being passed through organic compound is 0.1-5L/min, such as 0.1L/min, 0.5L/ min、1L/min、1.3L/min、1.6L/min、2L/min、2.5L/min、3L/min、3.5L/min、4L/min、4.5L/min Or 5L/min etc..
Preferably, step (3) time for being passed through organic compound is 0.5-10h, for example, 0.5h, 1h, 1.5h, 2h, 2.3h, 3h, 4h, 4.5h, 5h, 6h, 6.5h, 7h, 8h, 9h or 10h etc..
As the further preferred technical scheme of the method for the invention, the described method comprises the following steps：
(1) lithium source, ferric phosphate, dopant and carbon source are subjected to dispensing, obtain compound；
(2) above-mentioned compound is mixed with graphene, dispersant, deionized water, grinding distribution 2h-20h, wherein, go from The quality of sub- water is 1-6 times of above-mentioned mixture quality, obtains the uniform slurry of grinding distribution；
(3) it is spray-dried using the uniform slurry of grinding distribution, spray dryer inlet temperature is 200-350 DEG C, Outlet temperature is not less than 70 DEG C, obtains the secondary spherical ferric lithium phosphate precursor being made up of primary particle；
(4) above-mentioned secondary spherical ferric lithium phosphate precursor is placed in rotary furnace, rotated with 1-10r/min, with 1-10 DEG C/ Min is warming up to 600-750 DEG C, and constantly organic compound gas 0.5- is passed through with 0.1-5L/min flow velocitys under protective atmosphere 10h, growth in situ graphene is carried out, obtains the spherical composite of graphene-based LiFePO4.
The third aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes the composite wood of first aspect Material is used as active material, can add additional conductive agent, can not also add additional conductive agent.
Compared with prior art, the present invention has the advantages that：
(1) present invention passes through " graphene mixes-spheroidization-CVD growth in situ graphene with LFP precursor molecule levels " etc. Series technique, the spherical composite of the graphene-based LiFePO4 of high conductance is prepared, two states are included in the composite Graphene, a kind of is the graphene for being collectively formed with LiFePO4 primary particle, and another kind is CVD growth in situ by once The graphene layer for the secondary spherical particle surface that grain is formed.
(2) by adding graphene in LFP precursor pulps, the compactness between spherical LFP internal particles can be improved And electric conductivity, tap density is in 1.5g/cm3More than, be advantageous to improve nanoscale LFP processing characteristics, reduce LFP internal resistances, carry Its high multiplying power, cryogenic property, it is low to solve carbon content during preparing nano-level sphere LFP using conventional carbon source in the prior art When poorly conductive；When carbon content is high ball interior it is hollow it is more, tap density is not high " the problem of.
(3) in spherical LFP presomas sintering process, graphene CVD growth in situ was both inhibited in LFP spherome surfaces The reunion of primary particle improves electric conductivity again when LFP is sintered, its powder conductivity rate up to more than 1S/cm, improve 100 times with On；Compared with LFP powder surface in situ growth graphene after normal sintering, graphene growth is evenly, process is simpler, effect More preferably.In LFP battery applications, LFP spherome surfaces coat a layer graphene, inhibit the pair of LFP and electrolyte anti-well Should, it will be apparent that improve its high temperature storage and high temperature cyclic performance.And it can not add and lead because electric conductivity is fine, in its battery applications Electric agent, this is advantageous to further improve solid content with slurry, economic and environment-friendly.
(4) lithium ion is prepared as positive electrode active materials using the spherical composite of graphene-based LiFePO4 of the present invention Battery, it can add or save additional conductive agent.In the case of adding additional conductive agent, obtained lithium ion battery is in normal temperature 1C Gram volume in more than 145mAh/g, 1000 weeks capability retentions of normal temperature more than 92%, 20C/1C capability retentions 95% with On, -20 DEG C of low temperature：0.2C capability retentions are more than 80%；In the case of adding additional conductive agent, obtained lithium ion Battery still has good capacity, circulation and cryogenic property, in normal temperature 1C gram volumes in more than 143mAh/g, normal temperature 1000 weeks Capability retention is more than 90%, and 20C/1C capability retentions are more than 91%, -20 DEG C of low temperature：0.2C capability retentions exist More than 75%.
Brief description of the drawings
Fig. 1 is the SEM spectrum of the spherical composite of the high graphene-based LiFePO4 of conductance in the embodiment of the present invention 1；
Fig. 2 is the section SEM of the spherical composite of the high graphene-based LiFePO4 of conductance in the embodiment of the present invention 1；
Fig. 3 is the 0.1C charge and discharges first of the spherical composite of the high graphene-based LiFePO4 of conductance in the embodiment of the present invention 1 Electric curve；
Fig. 4 is the 0.5C cycle performances of the spherical composite of the graphene-based LiFePO4 of high conductance of the embodiment of the present invention 1 Curve.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1
(1) monohydrate lithium hydroxide, ferric phosphate, magnesia and glucose are mixed and carries out dispensing, in molar ratio Li:Fe:P: Mg=1.02:1:1.02:0.01 and carbon content be 0.8wt.%, carry out dispensing；
(2) above-mentioned (1) is expected to mix with graphene conductive liquid, polyethylene glycol, deionized water, grinding distribution 10h, ground Mill is uniformly dispersed, the suitable slurry of particle diameter, and wherein the weight of polyethylene glycol is the 0.2% of above-mentioned (1) material, the weight of deionized water For 4 times of above-mentioned (1) material；
(3) gained slurry being carried out into the fluid spray of pneumoelectric combined type two to dry, spray dryer inlet temperature is 300 DEG C, Outlet temperature is 100 DEG C, obtains the spherical lithium iron phosphate precursor that aggregate particle size is 5 μm；
(4) above-mentioned spherical lithium iron phosphate precursor is placed in rotary furnace, rotated with 1r/min, is warming up to 5 DEG C/min 700 DEG C, continue to be passed through propylene gas 2h with 0.5L/min flow velocitys, carry out growth in situ graphene, it is 70nm that primary particle size, which is made, Aggregate particle size is 5 μm of the spherical composite of the graphene-based LiFePO4 of high conductance.
Fig. 1 is the SEM spectrum of the spherical composite of the high graphene-based LiFePO4 of conductance in the present embodiment, can from Fig. 1 Go out, obtained material is spherical, and for primary particle in 70nm or so, aggregate particle size is 5 μm or so.
Fig. 2 is the section SEM of the spherical composite of the high graphene-based LiFePO4 of conductance in the present embodiment, can from Fig. 2 Go out very closely knit between ball interior primary particle.
Fig. 3 is the 0.1C first charge-discharges of the spherical composite of the high graphene-based LiFePO4 of conductance in the embodiment of the present invention Curve, from figure 3, it can be seen that its capacity is very high, discharge capacity reaches 169.1mAh/g to 0.1C first.
Fig. 4 is that the 0.5C cycle performances of the spherical composite of the high graphene-based LiFePO4 of conductance in the embodiment of the present invention are bent Line, as can be seen from Figure 4 its capacity is high and good cycle, and discharge capacity be 155.8mAh/g to 0.5C first, circulation 20 weeks Capability retention is 104.2% afterwards.
Embodiment 2
(1) by lithium carbonate, ferric phosphate, niobium oxalate and sucrose, Li in molar ratio:Fe:P:Nb=1.02:1:1.03:0.005 And carbon content is 0.7wt.%, dispensing is carried out；
(2) above-mentioned (1) is expected to mix with graphene oxide conduction liquid, polyvinyl alcohol, deionized water, grinding distribution 6h, obtained To the suitable slurry of particle diameter, the wherein weight of polyvinyl alcohol is the 0.25% of above-mentioned (1) material, and the weight of deionized water is above-mentioned (1) 4 times of material；
(3) gained slurry is subjected to two fluid spray dryings, spray dryer inlet temperature is 260 DEG C, and outlet temperature is 70 DEG C, obtain the spherical lithium iron phosphate precursor that aggregate particle size is 6 μm；
(4) above-mentioned spherical lithium iron phosphate precursor is placed in rotary furnace, rotated with 1.5r/min, heated up with 10 DEG C/min To 700 DEG C, continue to be passed through acetylene gas 1h with 1L/min flow velocitys, carry out growth in situ graphene, it is 6 μm that aggregate particle size, which is made, The spherical composite of the high graphene-based LiFePO4 of conductance.
Embodiment 3
(1) by lithium carbonate+monohydrate lithium hydroxide, ferric phosphate and citric acid, Li in molar ratio:Fe:P:M=(0.5+ 0.53):1:1.02:0, wherein, doped chemical M is 0, carbon content 0.5wt.%, carries out dispensing；
(2) above-mentioned (1) is expected to mix with graphene conductive liquid, polyvinylpyrrolidone, deionized water, grinding distribution 20h, It is uniformly dispersed, the suitable slurry of particle diameter, wherein the weight of polyvinylpyrrolidone is the 0.3% of above-mentioned (1) material, deionization The weight of water is 4 times of above-mentioned (1) material；
(3) gained slurry is subjected to four fluid spray dryings, spray dryer inlet temperature is 280 DEG C, and outlet temperature is 80 DEG C, obtain the spherical lithium iron phosphate precursor that aggregate particle size is 6 μm；
(4) above-mentioned spherical lithium iron phosphate precursor is placed in rotary furnace, rotated with 2r/min, is warming up to 5 DEG C/min 750 DEG C, continue to be passed through ethane gas 2h with 0.1L/min flow velocitys, carry out growth in situ graphene, the height electricity that aggregate particle size is 6 μm Lead the spherical composite of graphene-based LiFePO4.
Embodiment 4
(1) monohydrate lithium hydroxide, ferric phosphate, titanium dioxide and glucose are mixed and carries out dispensing, in molar ratio Li:Fe: P:Ti=1.0:1:1.05:0.05 and carbon content be 1.5wt.%, carry out dispensing；
(2) above-mentioned (1) is expected to mix with graphene powder, polyvinyl alcohol, deionized water, grinding distribution 15h, ground It is uniformly dispersed, the suitable slurry of particle diameter, wherein the weight of polyvinyl alcohol is the 2% of above-mentioned (1) material, and the weight of deionized water is upper State (1) material 6 times；
(3) gained slurry being carried out into the fluid spray of pneumoelectric combined type two to dry, spray dryer inlet temperature is 280 DEG C, Outlet temperature is 80 DEG C, obtains the spherical lithium iron phosphate precursor that aggregate particle size is 4 μm；
(4) above-mentioned spherical lithium iron phosphate precursor is placed in rotary furnace, 3r/min is rotated, and 750 are warming up to 5 DEG C/min DEG C, continue to be passed through propylene gas 5h with 2L/min flow velocitys, carry out growth in situ graphene, the height electricity that aggregate particle size is 4 μm is made Lead the spherical composite of graphene-based LiFePO4.
Embodiment 5
(1) monohydrate lithium hydroxide, ferric phosphate, vanadium oxide and glucose are mixed and carries out dispensing, in molar ratio Li:Fe:P:V =1.05:1:1.04:1 and carbon content be 1wt.%, carry out dispensing；
(2) above-mentioned (1) is expected to mix with graphene conductive liquid, glucose, deionized water, grinding distribution 4h, ground It is uniformly dispersed, the suitable slurry of particle diameter, wherein the weight of glucose is the 1% of above-mentioned (1) material, and the weight of deionized water is above-mentioned (1) 2.5 times of material；
(3) gained slurry being carried out into the fluid spray of pneumoelectric combined type two to dry, spray dryer inlet temperature is 325 DEG C, Outlet temperature is 90 DEG C, obtains the spherical lithium iron phosphate precursor that aggregate particle size is 5 μm；
(4) above-mentioned spherical lithium iron phosphate precursor is placed in rotary furnace, rotated with 5r/min, is warming up to 2 DEG C/min 650 DEG C, continue to be passed through acetylene gas 8h with 3L/min flow velocitys, carry out growth in situ graphene, the height that aggregate particle size is 5 μm is made The spherical composite of the graphene-based LiFePO4 of conductance.
Comparative example 1
(1) by monohydrate lithium hydroxide, ferric orthophosphate, magnesia and glucose, Li in molar ratio:Fe:P:M=1.02:1: 1.02:0.01, carbon content 1.6%, it is added in ball mill, ball milling 1h, then Ultrafine Grinding 6h again, obtains particle diameter and suitably starch Material；
(2) gained slurry is subjected to two fluid spray dryings, spray dryer inlet temperature is 280 DEG C, and outlet temperature is 100 DEG C, obtain the spherical lithium iron phosphate precursor that aggregate particle size is 6 μm；
(3) above-mentioned spherical lithium iron phosphate precursor is placed in roller kilns, is sintered with 700 DEG C of insulation 12h, is made one Secondary particle diameter is 100-300nm, and aggregate particle size is 6 μm of ball shape ferric phosphate lithium material.
The material obtained to embodiment 1-5 and comparative example 1 is assembled into as positive active material using following methods 18650PC：
The preparation of positive plate：In 5L mixers, positive active material, binding agent PVDF, conductive agent super-P are pressed 94:3:3 (in addition, embodiment 3 has positive active material, binding agent PVDF by 97:3 carry out dispensing, without conductive agent, carry out Contrast experiment, labeled as reference examples 3；Comparative example 1 has positive active material, binding agent PVDF by 97:3 carry out dispensing, do not have to Conductive agent, contrast experiment is carried out, labeled as reference examples 1) positive pole dispensing is carried out under oil system and vacuum condition, acquisition is uniform just Pole slurry, the anode sizing agent prepared is uniformly coated on plus plate current-collecting body Al paper tinsels, obtains positive plate.
The preparation of negative plate：By graphite, thickener CMC, binding agent SBR, conductive powdered carbon by weight 95:1:2:2 in water System is lower to carry out cathode blending, obtains uniform cathode size, the cathode size prepared is uniformly coated on into negative current collector Cu On paper tinsel and cool down, obtain negative plate.
The preparation of lithium ion battery：Will positive plate, negative plate and membrane winding according to made from above-mentioned technique prepare lithium from Sub- battery core, nonaqueous electrolytic solution is injected, prepare 18650PC cylindrical batteries, wherein, nonaqueous electrolytic solution uses concentration as 1.0mol/L's LiPF6As electrolyte, volume ratio is used as 1:1 ethylene carbonate, the mixture of diethyl carbonate are as nonaqueous solvents.
The lithium ion battery prepared to above-described embodiment and comparative example carries out related processing, electric performance test, and table 1 below is Corresponding test data.
Table 1
As known from Table 1, spheroidization and then CVD are former again after graphene is mixed with LFP precursor molecule levels using the present invention Position growth graphene made from the spherical composite of the high graphene-based LiFePO4 of conductance, can take into account well material gram volume, The performance such as low temperature, multiplying power and processing, circulation.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (10)

1. a kind of spherical composite of graphene-based LiFePO4, it is characterised in that the composite is included by primary particle The secondary spherical particle of composition, and it is grown in the graphene of the secondary spherical particle surface；
Wherein, the primary particle is the lithium iron phosphate particles comprising graphene.
2. composite according to claim 1, it is characterised in that the particle diameter of the primary particle is 20-300nm；
Preferably, the median of the secondary spherical particle is 3-9 μm；
Preferably, the graphene included in the primary particle accounts for the 1-5wt.% of composite gross mass, preferably 1- 2wt.%；
Preferably, the number of plies of the graphene of the secondary spherical particle surface is grown in for individual layer or less than 10 layers.
3. composite according to claim 1 or 2, it is characterised in that the secondary median of the composite is 3-9μm；
Preferably, the powder conductivity rate of the composite is in more than 1S/cm.
4. the preparation method of the composite as described in claim any one of 1-3, it is characterised in that methods described includes following Step：
(1) the ferric lithium phosphate precursor slurry for including graphene is prepared；
(2) it is spray-dried, obtains the secondary spherical ferric lithium phosphate precursor being made up of primary particle；
(3) secondary spherical ferric lithium phosphate precursor is placed in reacting furnace, is warming up to 600-750 DEG C, led under protective atmosphere Enter organic compound, carry out growth in situ graphene, obtain the spherical composite of graphene-based LiFePO4.
5. according to the method for claim 4, it is characterised in that step (1) the LiFePO4 forerunner for including graphene Somaplasm material is prepared via a method which to obtain：
(A) lithium source, ferric phosphate, optional dopant and optional carbon source are subjected to dispensing, obtain compound；
(B) compound is mixed with graphene, optional dispersant and deionized water, grinding distribution, obtains including graphene Ferric lithium phosphate precursor slurry.
6. according to the method for claim 5, it is characterised in that step (A) lithium source, ferric phosphate and optional dopant According to mol ratio Li:Fe:P:M=(1.0-1.1):1:(1-1.05):(0-0.02) carries out dispensing, wherein, M is in dopant Doped chemical；
Preferably, step (A) described lithium source includes monohydrate lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium oxalate or fluorination Any a kind or at least two kinds of of combination in lithium；
Preferably, step (A) described dopant is any a kind or at least two kinds of in Mg, Mn, Ti, V, Nb, Ni or Co compound Combination；
Preferably, in step (A), using the gross mass of lithium source, ferric phosphate, optional dopant and optional carbon source as 100wt.% Meter, the percentage that the carbon source accounts for gross mass is 0wt.%-1.5wt.%；
Preferably, step (A) described carbon source includes ascorbic acid, cellulose, polypropylene, epoxy resin, sucrose, glucose, fruit 1 kind or at least two kinds of of combination in sugar, citric acid, polyethylene glycol, starch, phenolic resin；
Preferably, the percentage that step (B) described graphene accounts for mixture quality is 0.1-1.5wt.%；
Preferably, the percentage that step (B) described dispersant accounts for mixture quality is 0-2wt.%；
Preferably, the quality of step (B) described deionized water is 1-6 times of mixture quality；
Preferably, step (B) described graphene is included in graphene powder, graphene conductive liquid, graphene oxide conduction liquid Any a kind or at least two kinds of of combination；
Preferably, step (B) described dispersant is in glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone or polyvinyl alcohol Any a kind or at least two kinds of of combination；
Preferably, the time of step (B) described grinding distribution is 2-20h.
7. according to the method described in claim any one of 4-6, it is characterised in that step (2) it is described spray drying for two fluids, Any a kind in the fluid of pneumoelectric combined type two, four fluid sprays；
Preferably, when step (2) carries out the spray drying, the inlet temperature of spray dryer is 200-350 DEG C, outlet temperature Not less than 70 DEG C.
8. according to the method described in claim any one of 4-7, it is characterised in that step (3) described reacting furnace is rotary furnace, and Rotary furnace is with 1-10r/min rotational speed；
Preferably, the heating rate of step (3) described reacting furnace is 1-10 DEG C/min；
Preferably, step (3) described protective atmosphere be argon gas atmosphere, nitrogen atmosphere or hydrogen atmosphere in any a kind or extremely Few 2 kinds combination atmosphere；
Preferably, step (3) described organic compound includes any in methane, ethane, ethene, acetylene, acetone, benzene and toluene 1 kind or at least two kinds of of combination；
Preferably, step (3) flow velocity for being passed through organic compound is 0.1-5L/min；
Preferably, step (3) time for being passed through organic compound is 0.5-10h.
9. according to the method described in claim any one of 4-8, it is characterised in that the described method comprises the following steps：
(1) lithium source, ferric phosphate, dopant and carbon source are subjected to dispensing, obtain compound；
(2) above-mentioned compound is mixed with graphene, dispersant, deionized water, grinding distribution 2h-20h, wherein, deionized water Quality be 1-6 times of above-mentioned mixture quality, obtain the uniform slurry of grinding distribution；
(3) it is spray-dried using the uniform slurry of grinding distribution, spray dryer inlet temperature is 200-350 DEG C, outlet Temperature is not less than 70 DEG C, obtains the secondary spherical ferric lithium phosphate precursor being made up of primary particle；
(4) above-mentioned secondary spherical ferric lithium phosphate precursor is placed in rotary furnace, rotated with 1-10r/min, with 1-10 DEG C/min 600-750 DEG C is warming up to, organic compound gas 0.5- is constantly passed through with 0.1-5L/min flow velocitys under protective atmosphere 10h, growth in situ graphene is carried out, obtains the spherical composite of graphene-based LiFePO4.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes answering described in claim any one of 1-3 Condensation material does not add additional conductive agent as active material.
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108163828A (en) * 2018-01-02 2018-06-15 乳源东阳光磁性材料有限公司 A kind of preparation method of spherical lithium iron phosphate anode material
CN108963255A (en) * 2018-06-01 2018-12-07 湖南国盛石墨科技有限公司 A kind of preparation method of the conduction liquid of containing graphene
CN109037659A (en) * 2018-09-04 2018-12-18 贝特瑞（天津）纳米材料制造有限公司 A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material
CN109920979A (en) * 2017-12-12 2019-06-21 宁德时代新能源科技股份有限公司 Positive plate and electrochemical cell
CN110429277A (en) * 2019-06-28 2019-11-08 合肥国轩高科动力能源有限公司 A kind of preparation method of the lithium iron phosphate positive material of high-pressure solid high rate capability
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EP3770996A1 (en) * 2019-07-23 2021-01-27 Formosa Plastics Transport Corporation Method for manufacturing lithium iron phosphate/carbon composite cathode material for secondary lithium ion battery
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683697A (en) * 2012-05-14 2012-09-19 中南大学 Preparation method of graphene-based LiFePO4/C composite material
CN104934608A (en) * 2015-04-13 2015-09-23 青岛科技大学 Preparation method of in-situ graphene coated lithium ion battery cathode material
CN105742629A (en) * 2014-12-09 2016-07-06 北京有色金属研究总院 In-situ preparation method of positive electrode material lithium iron phosphate/graphene compound for lithium-ion battery
CN106229505A (en) * 2016-08-17 2016-12-14 深圳市贝特瑞纳米科技有限公司 A kind of high-density spherical nano lithium iron phosphate material and preparation method thereof and the lithium ion battery comprising it
CN106602006A (en) * 2016-11-23 2017-04-26 深圳市山木新能源科技股份有限公司 Graphene and lithium iron phosphate composite material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683697A (en) * 2012-05-14 2012-09-19 中南大学 Preparation method of graphene-based LiFePO4/C composite material
CN105742629A (en) * 2014-12-09 2016-07-06 北京有色金属研究总院 In-situ preparation method of positive electrode material lithium iron phosphate/graphene compound for lithium-ion battery
CN104934608A (en) * 2015-04-13 2015-09-23 青岛科技大学 Preparation method of in-situ graphene coated lithium ion battery cathode material
CN106229505A (en) * 2016-08-17 2016-12-14 深圳市贝特瑞纳米科技有限公司 A kind of high-density spherical nano lithium iron phosphate material and preparation method thereof and the lithium ion battery comprising it
CN106602006A (en) * 2016-11-23 2017-04-26 深圳市山木新能源科技股份有限公司 Graphene and lithium iron phosphate composite material and preparation method thereof

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109920979A (en) * 2017-12-12 2019-06-21 宁德时代新能源科技股份有限公司 Positive plate and electrochemical cell
CN108163828A (en) * 2018-01-02 2018-06-15 乳源东阳光磁性材料有限公司 A kind of preparation method of spherical lithium iron phosphate anode material
CN108963255A (en) * 2018-06-01 2018-12-07 湖南国盛石墨科技有限公司 A kind of preparation method of the conduction liquid of containing graphene
CN110817851A (en) * 2018-08-08 2020-02-21 福建海峡石墨烯产业技术研究院有限公司 Preparation method of multi-edge graphene and aluminum ion battery prepared by same
CN109037659A (en) * 2018-09-04 2018-12-18 贝特瑞（天津）纳米材料制造有限公司 A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material
CN110429277A (en) * 2019-06-28 2019-11-08 合肥国轩高科动力能源有限公司 A kind of preparation method of the lithium iron phosphate positive material of high-pressure solid high rate capability
EP3770996A1 (en) * 2019-07-23 2021-01-27 Formosa Plastics Transport Corporation Method for manufacturing lithium iron phosphate/carbon composite cathode material for secondary lithium ion battery
CN111682202A (en) * 2019-09-02 2020-09-18 重庆特瑞电池材料股份有限公司 Method for synthesizing rodlike lithium iron phosphate by PVA (polyvinyl alcohol) -assisted two-fluid spraying solid phase
CN111682202B (en) * 2019-09-02 2022-12-27 重庆特瑞电池材料股份有限公司 Method for synthesizing rodlike lithium iron phosphate by PVA (polyvinyl alcohol) -assisted two-fluid spraying solid phase
CN114229818A (en) * 2021-12-23 2022-03-25 沈阳国科金能科技有限公司 Preparation method of in-situ doped graphene low-temperature lithium iron phosphate cathode material
CN114665076A (en) * 2022-03-25 2022-06-24 湖北亿纬动力有限公司 Composite cathode material and preparation method and application thereof
CN114784240A (en) * 2022-04-11 2022-07-22 厦门海辰新能源科技有限公司 Graphene-carbon-coated lithium iron phosphate positive electrode material and preparation method and application thereof
CN114784240B (en) * 2022-04-11 2023-09-22 厦门海辰储能科技股份有限公司 Graphene-carbon coated lithium iron phosphate positive electrode material, and preparation method and application thereof
CN115360478A (en) * 2022-07-13 2022-11-18 南昌大学 In-situ grown carbon nanotube type iron phosphate modified lithium-sulfur battery diaphragm and preparation method thereof, and lithium-sulfur battery
CN115360478B (en) * 2022-07-13 2024-03-29 南昌大学 In-situ growth carbon nanotube type ferric phosphate modified lithium sulfur battery diaphragm, preparation method thereof and lithium sulfur battery

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