CN106532013A - Lithium iron phosphate/carbon composite material for power battery, and preparation method and application of lithium iron phosphate/carbon composite material - Google Patents
Lithium iron phosphate/carbon composite material for power battery, and preparation method and application of lithium iron phosphate/carbon composite material Download PDFInfo
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- CN106532013A CN106532013A CN201611217372.5A CN201611217372A CN106532013A CN 106532013 A CN106532013 A CN 106532013A CN 201611217372 A CN201611217372 A CN 201611217372A CN 106532013 A CN106532013 A CN 106532013A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- 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 lithium iron phosphate/carbon composite material, and a preparation method and application thereof. The lithium iron phosphate/carbon composite material is formed by lithium iron phosphate and a complete and compact carbon film coating the surface of the lithium iron phosphate. The method comprises the steps of (1) mixing a lithium source, an iron source, a carbon source and an optional doping element source and adding a solvent for grinding and drying to obtain a precursor; (2) crushing the precursor until the particle sizes D50 are 2-8 microns; (3) carrying out roasting under the condition of introducing a gaseous organic carbon source and an inert gas to obtain a first coated product; (4) crushing the first coated product until the particle sizes D50 are 1-6 microns; and (5) carrying out roasting under the condition of introducing the gaseous organic carbon source and the inert gas to obtain a second coated product, namely the lithium iron phosphate/carbon composite material. Through coordination of process steps and control of parameters, the complete and compact carbon film can be formed on the surfaces of lithium iron phosphate particles, side reaction of the particles and an electrolyte is effectively relieved and the high-temperature performance of a battery is significantly improved.
Description
Technical field
The invention belongs to electrode material synthesis field, is related to a kind of positive electrode, Preparation Method And The Use, more particularly to
A kind of lithium iron phosphate/carbon composite material, its preparation method and the purposes in electrokinetic cell.
Background technology
China has become the big automobile production state of the first in the world and country of consumption, it is contemplated that the passenger car in the year two thousand thirty Chinese automobile
Recoverable amount will reach 2.5 hundred million.However, with energy-saving and emission-reduction, reducing energy dependence and being increasingly becoming international automobile industry and ring
Industrial expansion trend is protected, oil price rises steadily the pressure brought to auto industry in addition, Chinese Government had formulated phase in recent years
The energy-conservation answered and new-energy automobile development strategy.New-energy automobile builds sustainable development low-carbon (LC) as development fungible energy source
An important ring of society, is increasingly paid much attention to by countries in the world, and new-energy automobile is also formally listed in by the Chinese government
One of seven great strategy industries, based on reasons such as the feature of environmental protection, energy securities, it is me to greatly develop new-energy automobile new industry
The fundamental state policy of state, since 2013, National Development and Reform Committee, the Ministry of Finance, Ministry of Industry and Information and Deng Ge great ministries and commissions of the Department of Science and Technology go out successively
A series of encouragement of platform and the policies of new-energy automobile development are promoted, including the great number subsidy in new-energy automobile acquisition price,
And the not policy favour such as restricting the number of not restricting driving.
The core component of new-energy automobile is electrokinetic cell system, it is contemplated that the problem of security, at present big portion on the market
Sub-power battery is based on ferric phosphate lithium cell, this is because the P-O keys in LiFePO4 crystal are firm, it is difficult to decompose, even if
Also structural breakdown heating or oxidizing species will not be formed as cobalt acid lithium in high temperature or when overcharging, therefore possesses good
Security.Lithium iron phosphate dynamic battery at normal temperatures, cycle life reach more than 2000 times, and the theoretical life-span is up to 8～10
Year, but in summer, automobile is typically exposed to outdoor, and, generally between 30 DEG C～40 DEG C, the temperature of sun direct projection is more for outdoor temperature
Be up to 45 DEG C～75 DEG C, at such high temperatures battery storage, work when can aggravate as cathode material LiFePO4 and
The side reaction of electrolyte, so that the iron ion dissolution in LiFePO4, the iron ion of dissolution is through barrier film in anode surface
Obtain electronics and become iron simple substance being deposited on anode film table, so as to greatly be degrading the performance of battery, thus LiFePO4 is electric
The high-temperature behavior in pond is increasingly paid close attention to by battery and electric automobile producer, and the high-temperature behavior gesture for improving LiFePO 4 material exists
Must go.
102867955 B of CN disclose a kind of preparation method of ferric lithium phosphate precursor, comprise the following steps：First by iron
Source, lithium source, phosphorus source are according to mol ratio 1:1:1 ratio is well mixed, and is calcined after adding appropriate doped chemical, is prepared into
Preliminary ferric lithium phosphate precursor, then using two-period form grinding mode, preliminary obtained presoma is first carried out just by first paragraph
Level is crushed, and certified products enter secondary nano grinder, while the carbon source of preliminary crushing is uniformly added in separating twice charging,
Which is made to be mixed with carbon source while crushing, and fully making contact, nanoscale mixing is reached, LiFePO4 forerunner is obtained
Body.Preferably, chemical property is good, and internal resistance is than conventional high-temperature solid phase method for the uniformity of the lithium iron phosphate positive material for preparing
Product reduces by 50%, and high magnification brings up to 30C electric discharges from traditional highest 20C, and battery processing characteristics is strong.But, the multiplying power of high temperature
Performance and high temperature cyclic performance are poor, it is impossible to meet the demand of practical application.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of lithium iron phosphate/carbon is compound
Material, Preparation Method And The Use.There is one layer of complete and fine and close carbon on the surface of the lithium iron phosphate/carbon composite material of the present invention
Film, effectively alleviates the side reaction of particle and electrolyte, the initial discharge specific capacity of obtained battery in more than 137.2mAh/g,
60 DEG C of high temperature storages capacity surplus ratio of 7 days is more than 96.2%, and capacity restoration rate is more than 97.5%；60 DEG C of circulations of high temperature
Circulation cycle to capacity surplus ratio≤80% is more than 1362 cycles.
It is that, up to above-mentioned purpose, the present invention is employed the following technical solutions：
In a first aspect, the present invention provides a kind of preparation method of lithium iron phosphate/carbon composite material, methods described includes following
Step：
(1) lithium source, source of iron, phosphorus source and optional doped chemical source are mixed to get into material, add solvent to be ground, so
After be dried, obtain presoma；
(2) presoma for obtaining step (1) is crushed, and is 2 μm～8 μm to granularity D50；
(3) step (2) is crushed the material roasting under conditions of gaseous state organic carbon source and inert gas is passed through for obtaining, is obtained
To the first cladding product；
(4) the first cladding product that step (3) is obtained is crushed, is 1 μm～6 μm to granularity D50；
(5) step (4) is crushed the material roasting under conditions of gaseous state organic carbon source and inert gas is connected with for obtaining, is obtained
To the second cladding product, i.e. lithium iron phosphate/carbon composite material.
Preferably, step (1) lithium source, source of iron, phosphorus source and optional doped chemical source are according to elemental lithium:Ferro element:
P elements:The mol ratio (0.95～1.05) of doped chemical:(0.95～1.05):(0.95～1.05):(0～0.05) is mixed
Close, molar ratio can such as be 0.95:1:0.95:0、0.95:1:0.98:0、0.95:1:0.95:0.03、0.95:0.95:1:
0.02、0.95:0.98:1:0、0.98:0.96:1:0.04、1:1:0.95:0、1:1:1:0、1:1:1:0.01、1:1:1:0.03、
1:1:1:0.05、0.95:1:1:0.025 or 1:1:0.98:0.01 etc..
Heretofore described " optional doped chemical source " refers to：Doped chemical source can be added, it is also possible to without doping
Element source.
Preferably, step (1) lithium source includes lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium nitrate, lithium oxalate, vinegar
In sour lithium or lithium citrate any one or at least two mixture, mixture typical case but non-limiting examples have：
The mixture of the mixture of lithium hydroxide and lithium dihydrogen phosphate, lithium hydroxide and lithium nitrate, lithium dihydrogen phosphate and lithium oxalate it is mixed
Compound, the mixture of lithium hydroxide, lithium dihydrogen phosphate and lithium nitrate, mixture of lithium nitrate, lithium oxalate and lithium acetate etc..But and
The above-mentioned lithium source enumerated is not limited to, what other were commonly used in the art can reach the lithium source of same effect can also be used for the present invention.
Preferably, during step (1) source of iron includes ferric phosphate, ferrous oxalate, ferric acetate, di-iron trioxide or ferric nitrate
Any one or at least two mixture, mixture typical case but non-limiting examples have：Ferric phosphate and ferrous oxalate
Mixture, the mixture of ferric phosphate and ferric acetate, the mixture of ferric acetate and di-iron trioxide, ferric phosphate, ferrous oxalate and
The mixture of ferric acetate, mixture of ferric phosphate, ferric acetate and ferric nitrate etc..But the above-mentioned source of iron enumerated is not limited to, other
The commonly used in the art source of iron that can reach same effect can also be used for the present invention.
Preferably, step (1) phosphorus source include phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ferric phosphate or
In lithium dihydrogen phosphate any one or at least two mixture, mixture typical case but non-limiting examples have：Phosphoric acid
With the mixture of the mixture of ammonium dihydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate, phosphoric acid, ammonium dihydrogen phosphate and phosphoric acid hydrogen two
Mixture of ammonium etc..But the above-mentioned phosphorus source enumerated is not limited to, what other were commonly used in the art can reach the phosphorus source of same effect
Can be used for the present invention.
Preferably, step (1) the doped chemical source includes zinc source, manganese source, Tong Yuan, magnesium source, titanium source, zirconium source, silicon source, vanadium
Source, chromium source, in niobium source any one or at least two combination.By the addition of doped chemical so that crystal structure is produced
Certain defect, can be effectively improved the ionic conductivity of material, lift the embedded of Li ions, the efficiency of deintercalation.
Elemental lithium, ferro element, P elements and doped chemical in the present invention might not be only respectively by lithium source, source of iron, phosphorus
Source and doped chemical source provide, or two or more element comes from same raw material, such as biphosphate
Lithium not only can provide P elements but also can provide elemental lithium.
Preferably, step (1) solvent any one in water, methyl alcohol, ethanol, acetone or the isopropanol or at least
Two kinds of mixture, the mixture is typical but non-limiting examples have：The mixing of the mixture of water and methyl alcohol, water and ethanol
The mixture of the mixture of thing, methyl alcohol and ethanol, ethanol and acetone, methyl alcohol, ethanol, acetone, the mixture of isopropanol, water, first
Mixture of alcohol, ethanol, acetone and isopropanol etc..
Preferably, with the gross mass of step (1) material as 100% meter, the mass percent of step (1) solvent
For 40%～50%, such as 40%, 42%, 44%, 46%, 47.5%, 48%, 49% or 50% etc..
Preferably, step (1) mode that adopts of grinding is for ball milling, and time of the ball milling is 3h～5h, such as 3h,
3.2h, 3.4h, 3.5h, 3.6h, 3.8h, 4h, 4.2h, 4.3h, 4.5h, 4.8h or 5h etc..
Preferably, the mode that step (1) drying is adopted is spray drying.
Preferably, the device for adopting that is spray-dried is enclosed spray dryer.
Preferably, when being spray-dried, the temperature of air inlet is 220 DEG C～250 DEG C, such as 220 DEG C, 225 DEG C, 228
DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 245 DEG C or 250 DEG C etc..
Preferably, when being spray-dried, the temperature of air outlet is 70 DEG C～90 DEG C, such as 70 DEG C, 72 DEG C, 74 DEG C, 75
DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C or 90 DEG C etc..
In the present invention, step (2) is crushed to granularity D50 for 2 μm～8 μm, such as 2 μm, 3 μm, 3.5 μm, 4 μm, 5 μm, 5.5
μm, 6 μm, 7 μm or 8 μm etc..
In the present invention, step (4) is crushed to granularity D50 for 1 μm～6 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 4.5 μm, 5 μm
Or 6 μm etc..
Preferably, step (3) and during step (5) roasting, the gaseous state organic carbon source being passed through independently include methane, ethane,
In propane, cyclopropane, ethene, butylene or acetylene any one or at least two mixture, the mixture is typical but non-
Limitative examples have：The mixture of the mixture of the mixture of methane and ethane, methane and propane, methane and cyclopropane, ethane
With the mixture of the mixture of ethene, ethane and acetylene, the mixture of ethane, propane and ethene, methane, ethane, ethene and fourth
Mixture of alkene etc..But the above-mentioned gaseous state organic carbon source enumerated is not limited to, other roastings in the present invention commonly used in the art
Temperature conditionss under (600 DEG C～800 DEG C i.e. of the present invention) cleavable can also be used for the present invention for the organic gas of carbon.
Preferably, step (3) and during step (5) roasting, the inert gas being passed through independently include nitrogen, helium, neon,
The gaseous mixture of any one or at least two gases in argon gas, Krypton, xenon or carbon dioxide.
Preferably, step (3) and during step (5) roasting, the flow of the gaseous state organic carbon source being passed through independently is 0.5L/
Min～10L/min, such as 0.5L/min, 1L/min, 1.5L/min, 2L/min, 3L/min, 4L/min, 4.5L/min, 5L/
Min, 6L/min, 7L/min, 8L/min, 8.5L/min, 9L/min or 10L/min etc..
Preferably, step (3) and during step (5) roasting, the temperature of roasting independently is 600 DEG C～800 DEG C, and such as 600
℃、620℃、625℃、635℃、645℃、660℃、670℃、680℃、700℃、720℃、725℃、735℃、750℃、
760 DEG C, 770 DEG C, 780 DEG C or 800 DEG C etc..
Preferably, step (3) and during step (5) roasting, time of roasting independently are 3h～15h, such as 3h, 4h, 5h,
6h, 7h, 8h, 9h, 10h, 12h, 13h, 14h or 15h etc..
During step (3) and step (5) are warming up to the temperature of the roasting, inert gas, the inertia are connected with
Gas includes the mixed of any one in nitrogen, helium, neon, argon gas, Krypton, xenon or carbon dioxide or at least two gases
Close gas.
Preferably, be warmed up to the temperature of the roasting of step (3) and step (5) heating rate independently be 2 DEG C/min～
20 DEG C/min, such as 2 DEG C/min, 3 DEG C/min, 5 DEG C/min, 8 DEG C/min, 10 DEG C/min, 12.5 DEG C/min, 13.5 DEG C/min,
15 DEG C/min, 16 DEG C/min, 17 DEG C/min, 18 DEG C/min, 19 DEG C/min or 20 DEG C/min etc..
Second aspect, the present invention provide the lithium iron phosphate/carbon composite material that method is prepared as described in relation to the first aspect, institute
State the carbon film that lithium iron phosphate/carbon composite material includes LiFePO4 and is coated on LiFePO4 surface.
Preferably, the phosphorus content of the lithium iron phosphate/carbon composite material is lithium iron phosphate/carbon composite material gross mass
1%～5%, such as 1%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.75%, 3%, 3.3%, 3.5%, 3.7%,
3.8%th, 4%, 4.5% or 5% etc..
The third aspect, the present invention provide a kind of positive pole, comprising the phosphorus described in second aspect in the raw material components of the positive pole
Sour iron lithium/carbon composite material is used as active material.
Fourth aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes the phosphorus described in second aspect
Sour iron lithium/carbon composite material.
The lithium ion battery of the present invention can be used as electrokinetic cell.
Compared with the prior art, the present invention has the advantages that：
The method of the present invention by first ferric lithium phosphate precursor being carried out being crushed to certain particle size, then in the synthesis of material
During be passed through a certain amount of cleavable at high temperature be carbon gaseous state organic carbon source carry out a carbon coating, crush afterwards, then
Being passed through the gaseous state organic carbon source that a certain amount of cleavable at high temperature is carbon again carries out secondary carbon coating, obtains lithium iron phosphate/carbon multiple
Condensation material.Gaseous state organic carbon source is passed through in the present invention carries out high temperature gas phase carbon coating twice, gaseous state organic carbon source one side conduct
Barrier, alleviates the phenomenon of growing up of primary particle of the material in building-up process, on the other hand contributes to being formed in particle surface
Fine and close vapor-phase thermal cracking carbon film.Crush for the first time and can obtain the suitable primary particle of granularity, be favorably improved it is follow-up once
The effect of carbon coating, then after second is crushed, part second particle can be caused to open, proceed secondary high-temperature gas phase
Carbon coating so that the particle surface not fully being coated to before is completely covered cladding, so as in lithium iron phosphate particles table
Face forms complete and fine and close carbon film, effectively alleviates the side reaction of particle and electrolyte so that the high-temperature behavior of battery is shown
Write and lifted, initial discharge specific capacity in more than 137.2mAh/g, 60 DEG C of high temperature storages capacity surplus ratio of 7 days 96.2% with
On, and capacity restoration rate is more than 97.5%；60 DEG C of high temperature was recycled to the circulation cycle of capacity surplus ratio≤80% at 1362 weeks
More than secondary.
Description of the drawings
Fig. 1 is the SEM figures of lithium iron phosphate/carbon composite material prepared by the embodiment of the present invention 1.
Specific embodiment
Technical scheme is further illustrated below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
By lithium carbonate, ferric phosphate, titanium dioxide according to mol ratio 1.05:1:0.01 is mixed, then Li:Fe:P:Ti=
1.05:1:1:0.01, and add water by the 40% of the material gross mass being mixed to get and carry out ball milling, slurry is taken out after 3h, enclosed is used
Spray dryer is dried, and intake air temperature arranges 250 DEG C, and air outlet temperature arranges 90 DEG C, obtains material A, material A is entered
Row is crushed, and is controlled D50 for 5 ± 1.0 μm, is obtained material B, and material B is heated up with 2 DEG C/min under the atmosphere of Ar gas, and according to
The flow of 5L/min is passed through methane gas, and temperature is incubated 15h after rising to 600 DEG C, obtains material C, and material C is crushed, control
D50 processed is 2.0 ± 1.0 μm, obtains material D, by material D in N2Heated up with 10 DEG C/min under the atmosphere of gas, and according to 0.5L/
The flow of min is passed through methane gas, and temperature is incubated 8h after rising to 750 DEG C, obtains the lithium iron phosphate positive material of carbon coated twice,
That is lithium iron phosphate/carbon composite material, the carbon content of the final lithium iron phosphate/carbon composite material of Jing test tests is 1.96%.
Embodiment 2
Lithium hydroxide, ferrous oxalate, phosphoric acid are compared into 0.95 according to you:1:0.95 is mixed, then Li:Fe:P=0.95:
1:0.95, and ball milling is carried out by 40% plus acetone of the material gross mass being mixed to get, slurry is taken out after 3h, it is dry with enclosed spraying
Dry machine is dried, and intake air temperature arranges 220 DEG C, and air outlet temperature arranges 70 DEG C, obtains material A, material A is carried out powder
It is broken, D50 is controlled for 7 ± 1.0 μm, obtain material B, by material B in N2Heated up with 20 DEG C/min under the atmosphere of gas, and according to
The flow of 0.5L/min is passed through ethylene gas, and temperature is incubated 10h after rising to 700 DEG C, obtains material C, and material C is crushed,
D50 is controlled for 5.0 ± 1.0 μm, material D is obtained, by material D in N2Heated up with 5 DEG C/min under the atmosphere of gas, and according to 2L/min
Flow be passed through methane gas, temperature is incubated 3h after rising to 800 DEG C, obtain the LiFePO4 of carbon coated twice, i.e. LiFePO4/
Carbon composite, the carbon content of the final lithium iron phosphate/carbon composite material of Jing test tests is 1.1%.
Embodiment 3
Lithium dihydrogen phosphate, di-iron trioxide, manganese acetate are compared into 1 according to you:0.95:0.05 is mixed, then Li:Fe:P:
Mn=1:0.95:1:0.05, and ball milling is carried out by 50% plus ethanol of the material gross mass being mixed to get, slurry is taken out after 5h,
It is dried with enclosed spray dryer, intake air temperature arranges 220 DEG C, air outlet temperature arranges 70 DEG C, obtains material A, will
Material A is crushed, and is controlled D50 for 4 ± 1.0 μm, is obtained material B, by material B under the atmosphere of Ar gas with 10 DEG C/min liters
Temperature, and the flow according to 8L/min is passed through propane gas, temperature is incubated 3h after rising to 800 DEG C, obtains material C, and material C is carried out
Crushing, D50 being controlled for 2.0 ± 1.0 μm, obtain material D, material D is heated up with 10 DEG C/min under the atmosphere of Ar gas, and according to
The flow of 10L/min is passed through cyclopropane gas, and temperature is incubated 10h after rising to 700 DEG C, obtains the LiFePO4 of carbon coated twice,
That is lithium iron phosphate/carbon composite material, it is 4.06% that Jing tests the carbon content of final lithium iron phosphate/carbon composite material.
Embodiment 4
By lithium hydroxide, ferric acetate, ammonium phosphate according to mol ratio 1.05:1:1 is mixed, then Li:Fe:P=1.05:1:
1, and ball milling is carried out by 45% plus methyl alcohol of the material gross mass being mixed to get, slurry is taken out after 4h, enclosed spray dryer is used
It is dried, intake air temperature arranges 230 DEG C, air outlet temperature arranges 80 DEG C, obtains material A, material A is crushed, controls
D50 processed is 6 ± 1.0 μm, obtains material B, and material B is heated up with 7 DEG C/min under the atmosphere of Ar gas, and according to the stream of 1L/min
Amount is passed through methane gas, and temperature is incubated 12h after rising to 650 DEG C, obtains material C, and material C is crushed, and controls D50 for 4.0
± 1.0 μm, material D is obtained, by material D in N2Heated up with 15 DEG C/min under the atmosphere of gas, and the flow according to 1.5L/min leads to
Enter cyclopropane gas, temperature is incubated 5h after rising to 700 DEG C, obtains the lithium iron phosphate positive material of carbon coated twice, i.e. ferric phosphate
Lithium/carbon composite material, the carbon content of the final lithium iron phosphate/carbon composite material of Jing test tests is 2.53%.
Embodiment 5
Lithium oxalate, ferric nitrate, ammonium dihydrogen phosphate are compared into 0.98 according to you:1:0.96 is mixed, then Li:Fe:P=
0.98:1:0.96, and ball milling is carried out by 50% plus isopropanol of the material gross mass being mixed to get, slurry is taken out after 3.5h, is used
Enclosed spray dryer is dried, and intake air temperature arranges 240 DEG C, and air outlet temperature arranges 75 DEG C, obtains material A, by thing
Material A is crushed, and is controlled D50 for 5 ± 1.0 μm, is obtained material B, by material B in N2Heated up with 17 DEG C/min under the atmosphere of gas,
And the flow according to 7L/min is passed through butene gas, temperature is incubated 6h after rising to 750 DEG C, obtains material C, and material C is carried out powder
It is broken, D50 is controlled for 3.0 ± 1.0 μm, obtain material D, by material D in N2Heated up with 3 DEG C/min under the atmosphere of gas, and according to 6L/
The flow of min is passed through methane gas, and temperature is incubated 8h after rising to 650 DEG C, obtains the LiFePO4 of carbon coated twice, i.e. ferric phosphate
Lithium/carbon composite material, the carbon content of the final lithium iron phosphate/carbon composite material of Jing test tests is 4.53%.
Embodiment 6
Lithium dihydrogen phosphate, ferric acetate, zirconium dioxide are compared into 1 according to you:1:0.03 is mixed, then Li:Fe:P:Zr=1:
1:1:0.03, and ball milling is carried out by 40% plus acetone of the material gross mass being mixed to get, slurry is taken out after 4.5h, is sprayed with enclosed
Mist drying machine is dried, and intake air temperature arranges 245 DEG C, and air outlet temperature arranges 85 DEG C, obtains material A, material A is carried out
Crushing, D50 being controlled for 6 ± 1.0 μm, obtain material B, material B is heated up with 12 DEG C/min under the atmosphere of Ar gas, and according to
The amount of 3L/min is passed through propane gas, and temperature is incubated 11h after rising to 700 DEG C, obtains material C, and material C is crushed, control
D50 is 3.0 ± 1.0 μm, obtains material D, and material D is heated up with 4 DEG C/min under the atmosphere of He gas, and according to the amount of 9L/min
Cyclopropane gas is passed through, temperature is incubated 7h after rising to 750 DEG C, obtains the LiFePO4 of carbon coated twice, i.e. lithium iron phosphate/carbon multiple
Condensation material, it is 3.88% that Jing tests the carbon content of final lithium iron phosphate/carbon composite material.
Comparative example 1
By lithium dihydrogen phosphate, ferrous oxalate, titanium dioxide in molar ratio 1:1:0.01 is mixed to get presoma material, then
Li:Fe:P:Ti=1:1:1:0.01, add the 10% of presoma material gross mass glucose to be mixed, and press presoma
50% plus ethanol of material gross mass carries out ball milling, takes out slurry, be dried with enclosed spray dryer after 5h, air inlet temperature
Degree arranges 220 DEG C, and air outlet temperature arranges 70 DEG C, obtains material A, by material A in N2The lower 700 DEG C of constant temperature 12h of atmosphere of composition
Lithium iron phosphate/carbon composite material is obtained, it is 1.87% that Jing tests the carbon content of final lithium iron phosphate/carbon composite material.
Performance test：
(1) preparation of battery
The preparation of positive pole：
Using embodiment 1-6 and lithium iron phosphate/carbon composite material obtained in comparative example 1 is used as positive active material, respectively will
90g positive active materials, 5g binding agent Kynoar (PVDF) and 5g conductive agent Super-p are added to 50gN- methylpyrroles
In alkanone, then in de-airing mixer, stirring forms uniform anode sizing agent.The anode sizing agent is uniformly coated to into thickness
For the both sides of 18 μm of aluminium foil, then drying, roll-in at 150 DEG C, cut the positive pole that prepared size is 540 × 43.5mm, wherein
Containing about 5.2g active component LiFePO4/ C (lithium iron phosphate/carbon composite material).
The preparation of negative pole：
90g negative electrode active composition native graphites, 5g bonding agent Kynoar, 5g conductive agent carbon blacks are added to into 100gN-
In methyl pyrrolidone, then in de-airing mixer, stirring forms uniform cathode size.The cathode size is equably applied
Cloth in the both sides of the Copper Foil that thickness is 12 μm, then at 90 DEG C drying, roll-in, cut prepared size for the negative of 500 × 44mm
Pole, wherein containing about 3.8g active component native graphites.
The assembling of battery：
Above-mentioned positive and negative electrode and polypropylene screen are wound into the pole piece of a square lithium ion battery respectively, subsequently will
LiPF6EC/EMC/DEC=1 is dissolved in by the concentration of 1mol/L:1:Nonaqueous electrolytic solution is formed in 1 mixed solvent, this is electrolysed
During liquid is with the amount injection battery aluminum shell of 3.8g/Ah, sealing makes lithium rechargeable battery, using embodiment 1-6 and comparative example 1
Lithium iron phosphate/carbon composite material be numbered A1-A6, B1 successively respectively as battery made by positive active material.
(2) battery performance test
Two groups of identicals battery A1-A6 and B1 are prepared respectively, are named as A1-1, A1-2, A2-1, A2-2, A3-1, A3-
2nd, A4-1, A4-2, A5-1, A5-2, A6-1, A6-1, B1-1 and B1-2.Lithium ion battery obtained above is individually placed to into test
On cabinet, constant-current constant-voltage charging is carried out with 1C first in 25 DEG C of insulating boxs, charging upper limit is 3.65V；After shelving 20min, with 1C's
Electric current is discharged to 2.0V from 3.65V, records the discharge capacity first of battery, then carries out constant-current constant-voltage charging with 1C electric currents, fill
The electric upper limit is 3.65V.
By 2 (A1- of charged Li-ion batteries piles 1 (A1-1, A2-1, A3-1, A4-1, A5-1, A6-1 and B1-1) and group
2nd, A2-2, A3-2, A4-2, A5-2, A6-2 and B1-2) it is respectively placed in high-low temperature chamber, group 1 is deposited seven days under the conditions of 60 DEG C,
And the capacity surplus ratio and recovery rate of battery core after storage seven days are tested, group 2 carries out 1C high temperature circulations, voltage range at 60 DEG C
2.0V～3.65V, treats capacity surplus ratio less than 80% cabinet at present, and records cycle-index, concrete data see the table below
1 full battery high-temperature behavior Data Comparison of table
Data from upper table can be seen that the lithium iron phosphate/carbon composite material prepared using the method for the present invention
The initial discharge specific capacity of the battery for preparing positive pole as positive active material and being further assembled in more than 137.2mAh/g,
60 DEG C of high temperature storages capacity surplus ratio of 7 days is more than 96.2%, and capacity restoration rate is more than 97.5%；60 DEG C of circulations of high temperature
Circulation cycle to capacity surplus ratio≤80% is more than 1362 cycles.Knowable to contrast, initial discharge specific capacity, high temperature storage
Energy and high temperature cyclic performance are superior to the reference cell of comparative example 1, illustrate that the method for the present invention can significantly lift phosphoric acid
Chemical property and life-span at a high temperature of iron lithium dynamical battery.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office 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 implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, to the equivalence replacement and auxiliary element of 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 disclosure.
Claims (10)
1. a kind of preparation method of lithium iron phosphate/carbon composite material, it is characterised in that the method comprising the steps of：
(1) lithium source, source of iron, phosphorus source and optional doped chemical source are mixed to get into material, add solvent to be ground, Ran Hougan
It is dry, obtain presoma；
(2) presoma for obtaining step (1) is crushed, and is 2 μm～8 μm to granularity D50；
(3) step (2) is crushed into material roasting under conditions of gaseous state organic carbon source and inert gas is passed through for obtaining, obtains the
One cladding product；
(4) the first cladding product that step (3) is obtained is crushed, is 1 μm～6 μm to granularity D50；
(5) step (4) is crushed into material roasting under conditions of gaseous state organic carbon source and inert gas is passed through for obtaining, obtains the
Two cladding product, i.e. lithium iron phosphate/carbon composite materials.
2. method according to claim 1, it is characterised in that step (1) lithium source, source of iron, phosphorus source and optional mix
Miscellaneous element source is according to elemental lithium:Ferro element:P elements:The mol ratio (0.95～1.05) of doped chemical:(0.95～1.05):
(0.95～1.05):(0～0.05) is mixed；
Preferably, step (1) lithium source includes lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium nitrate, lithium oxalate, lithium acetate
In lithium citrate any one or at least two mixture；
Preferably, step (1) source of iron includes appointing in ferric phosphate, ferrous oxalate, ferric acetate, di-iron trioxide or ferric nitrate
Meaning it is a kind of or at least two mixtures；
Preferably, step (1) phosphorus source includes phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ferric phosphate or phosphoric acid
In dihydro lithium any one or at least two mixture；
Preferably, step (1) the doped chemical source include zinc source, manganese source, Tong Yuan, magnesium source, titanium source, zirconium source, silicon source, vanadium source,
In chromium source, niobium source any one or at least two combination；
Preferably, step (1) solvent is selected from any one in water, methyl alcohol, ethanol, acetone or isopropanol or at least two
Mixture；
Preferably, with the gross mass of step (1) material as 100% meter, the mass percent of step (1) solvent is
40%～50%.
3. method according to claim 1 and 2, it is characterised in that step (1) mode for adopting of grinding for ball milling,
The time of the ball milling is 3h～5h；
Preferably, the mode that step (1) drying is adopted is spray drying；
Preferably, the device for adopting that is spray-dried is enclosed spray dryer；
Preferably, when being spray-dried, the temperature of air inlet is 220 DEG C～250 DEG C；
Preferably, when being spray-dried, the temperature of air outlet is 70 DEG C～90 DEG C.
4. the method according to any one of claim 1-3, it is characterised in that when step (3) and step (5) roasting, be connected with
Gaseous state organic carbon source independently include methane, ethane, propane, cyclopropane, ethene, butylene or acetylene in any one or extremely
Few two kinds mixture；
Preferably, step (3) and during step (5) roasting, the inert gas being passed through independently includes nitrogen, helium, neon, argon
The gaseous mixture of any one or at least two gases in gas, Krypton, xenon or carbon dioxide；
Preferably, step (3) and during step (5) roasting, the flow of the gaseous state organic carbon source being passed through independently be 0.5L/min～
10L/min。
5. the method according to any one of claim 1-4, it is characterised in that when step (3) and step (5) roasting, roasting
Temperature independently be 600 DEG C～800 DEG C；
Preferably, step (3) and during step (5) roasting, the time of roasting independently is 3h～15h.
6. method according to claim 5, it is characterised in that step (3) and step (5) are warming up to the temperature of the roasting
During, it is connected with inert gas, the inert gas includes any one in nitrogen, argon gas or carbon dioxide or at least
The gaseous mixture of two kinds of gases；
Preferably, be warmed up to the temperature of the roasting of step (3) and step (5) heating rate independently be 2 DEG C/min～20 DEG C/
min。
7. the lithium iron phosphate/carbon composite material that the method as described in any one of claim 1-6 is prepared, it is characterised in that
The lithium iron phosphate/carbon composite material includes LiFePO4 and is coated on the carbon film on LiFePO4 surface.
8. lithium iron phosphate/carbon composite material according to claim 7, it is characterised in that the lithium iron phosphate/carbon composite wood
The phosphorus content of material for lithium iron phosphate/carbon composite material gross mass 1%～5%.
9. a kind of positive pole, it is characterised in that in the raw material components of the positive pole comprising the LiFePO4 described in claim 7 or 8/
Carbon composite is used as active material.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes the ferric phosphate described in claim 7 or 8
Lithium/carbon composite material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101237039A (en) * | 2008-01-08 | 2008-08-06 | 上海大学 | Method for synthesizing LiFePO4/C material based on chemical gas phase sediment auxiliary solid phase method |
| CN105428648A (en) * | 2015-11-27 | 2016-03-23 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing battery cathode material lithium iron phosphate |
| 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 |
| CN106252620A (en) * | 2016-08-17 | 2016-12-21 | 浙江美思锂电科技有限公司 | A kind of method that the CVD of employing low temperature prepares carbon-coated LiFePO 4 for lithium ion batteries positive electrode |
-
2016
- 2016-12-26 CN CN201611217372.5A patent/CN106532013A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101237039A (en) * | 2008-01-08 | 2008-08-06 | 上海大学 | Method for synthesizing LiFePO4/C material based on chemical gas phase sediment auxiliary solid phase method |
| CN105428648A (en) * | 2015-11-27 | 2016-03-23 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing battery cathode material lithium iron phosphate |
| 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 |
| CN106252620A (en) * | 2016-08-17 | 2016-12-21 | 浙江美思锂电科技有限公司 | A kind of method that the CVD of employing low temperature prepares carbon-coated LiFePO 4 for lithium ion batteries positive electrode |
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