CN105720256B - A kind of preparation method of lithium iron phosphate positive material - Google Patents
A kind of preparation method of lithium iron phosphate positive material Download PDFInfo
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- CN105720256B CN105720256B CN201610227167.0A CN201610227167A CN105720256B CN 105720256 B CN105720256 B CN 105720256B CN 201610227167 A CN201610227167 A CN 201610227167A CN 105720256 B CN105720256 B CN 105720256B
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- phosphate
- positive electrode
- electrode active
- lithium
- lithium iron
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- 239000000463 material Substances 0.000 title claims abstract description 28
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 31
- 235000019441 ethanol Nutrition 0.000 claims description 30
- 150000001298 alcohols Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- -1 phosphate ester Chemical class 0.000 claims description 15
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 159000000013 aluminium salts Chemical class 0.000 claims description 12
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 238000005253 cladding Methods 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical group [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims 1
- 239000005955 Ferric phosphate Substances 0.000 claims 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims 1
- 229960000935 dehydrated alcohol Drugs 0.000 claims 1
- 229960004756 ethanol Drugs 0.000 claims 1
- 229940032958 ferric phosphate Drugs 0.000 claims 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052493 LiFePO4 Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910010942 LiFP6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
Classifications
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation methods of lithium iron phosphate positive material, and this method comprises the following steps: (1) preparing LiFePO 4 material.(2) positive electrode active materials covering liquid is prepared.(3) it coats.The positive electrode of method preparation, has preferable electric conductivity and cycle performance, specific capacity with higher and longer service life.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of preparation method of lithium iron phosphate positive material.
Background technique
The rapid development of auto industry has pushed the progress and development of the industries such as global machinery, the energy, traffic, but fuel oil
For automobile while promoting the well-being of mankind, exhaust emissions also causes serious pollution to human residential environment.Environmental protection and energy shortage
It is required that having driven the development of electric car (EV) and power battery.Main problem existing for electric vehicle is price, driving at present
Mileage, power performance etc., and these problems are all closely related with battery technology, the research of battery technology and battery material is opened
Hair, which will develop it, to play a decisive role, thus finds exploitation high-energy-density, cheap, safe and reliable positive electrode to dynamic
The exploitation of power power supply lithium ion battery has very important significance.
Current commercialized lithium ion anode material is mainly with LiFePO4 (LiFePO4), ternary material (nickel cobalt manganese three
First material NCM, nickel cobalt aluminium ternary material NCA) and LiMn2O4 (LiMn2O4) etc. based on, wherein lithium manganate battery cycle life
Cycle life is worse under short and hot environment, and ternary material is as power battery that there are safety issues.LiFePO4 raw material
Price is low, and theoretical capacity is big, has extended cycle life, and is the generally acknowledged most promising product of lithium battery.
The disadvantage of ion and electron conduction difference for LiFePO4, general method of modifying are carbon coating, material
Grain nanosizing and metal ion mixing etc., the high rate performance of battery is improved by above method, improves its cyclical stability.Its
Middle nanosizing makes the poor processability of material, and doping vario-property technique is more complex, to be improved and developed.
Summary of the invention
The present invention provides a kind of preparation method of lithium iron phosphate positive material, the positive electrode prepared using this method, tool
There are preferable electric conductivity and cycle performance, specific capacity with higher and longer service life.
To achieve the goals above, the present invention provides a kind of preparation method of lithium iron phosphate positive material, and this method includes
Following steps:
(1) LiFePO 4 material is prepared
Lithium carbonate, ammonium dihydrogen phosphate, ferrous oxalate are weighed respectively according to the ratio of stoichiometric ratio 1:1:1, are added anhydrous
Ethyl alcohol is carried out after mixing with 400-500rpm revolving speed ball milling 6-10h, then obtains phosphorus in 70-90 DEG C of vacuum drying 10-20h
Sour iron lithium precursor；
380-420 DEG C of heat preservation 4-6h, continuation in the tube furnace of purity nitrogen atmosphere protection by ferric lithium phosphate precursor obtained
It is warming up to after 650-750 DEG C of calcining 6-10h and naturally cools to room temperature and obtain lithium iron phosphate positive material；
(2) positive electrode active materials covering liquid is prepared
Phosphate compounds are added in alcohols solvent, obtain phosphate ester solution；
Aluminium salt is added in the phosphate ester solution, which is dissolved in the alcohols solvent, and anti-with the phosphate compounds
Homogeneous clear solution should be obtained, reaction temperature is 40-80 DEG C, and the reaction time is 2-5 hours；
Addition acidity regulator adjusts the pH value of the homogeneous clear solution to 6-7, and acidity regulator can be ammonium hydroxide, carbon
One of sour hydrogen ammonium, ammonium carbonate, ammonium acetate, pyridine and triethylamine or more than one, the total additional amount of the acidity regulator is pressed
It is that 1:1-6:1 weighs to obtain the positive electrode active materials covering liquid according to N:Al molar ratio；
(3) it coats
The lithium iron phosphate positive material is uniformly mixed with the positive electrode active materials covering liquid, obtains solid-liquid mixing
Object；And
It by solidliquid mixture drying and is sintered, which can be room temperature naturally dry or heating, drying, as long as removal should
Solvent in mixture, the temperature of the heating, drying are preferably 60-100 DEG C.The sintering carries out in air, makes this
The organic group removal in predecessor is coated, the clad is generated.The sintering temperature is 450-750 DEG C, and sintering time is that 5-8 is small
When, anode composite material is obtained, which includes positive electrode active materials and be coated on the surface of positive electrode active material
Clad.
Preferably, the alcohols solvent be one of methanol, ethyl alcohol, propyl alcohol, n-butanol and isopropanol or more than one
Double solvents, the phosphate compounds general formula can be AnP(O)(OH)m, wherein A is carbon corresponding with the alcohol solvent molecules
At least one of oxygen groups, i.e. methoxyl group, ethyoxyl, propoxyl group, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；
The mass ratio of phosphate compounds and alcohols solvent is 1:5-1:25.
Preferably, aluminium salt be one of aluminium chloride, aluminum nitrate, aluminium isopropoxide and aluctyl or more than one.The alcohol is molten
Property the total additional amount of aluminium salt and alcohols solvent mass ratio be preferably 1:10-1:20.
Positive electrode active materials covering liquid in the present invention is a homogeneous clear solution, can be relatively easily in LiFePO4
Grain surface is respectively formed clad, so that each lithium iron phosphate particles surface is wrapped by layer cladding completely, further increases its electric conductivity
Energy and cyclical stability.Therefore the lithium iron phosphate positive material prepared by the present invention has higher when being used for lithium ion battery
The reversible capacity of electric discharge for the first time and longer service life.
Specific embodiment
Embodiment one
Lithium carbonate, ammonium dihydrogen phosphate, ferrous oxalate are weighed respectively according to the ratio of stoichiometric ratio 1:1:1, are added anhydrous
Ethyl alcohol is carried out after mixing with 400rpm revolving speed ball milling 6h, then obtains ferric lithium phosphate precursor in 70 DEG C of vacuum drying 10h
Powder.
By ferric lithium phosphate precursor obtained in the tube furnace of purity nitrogen atmosphere protection 380 DEG C of heat preservation 4h, be continuously heating to
Room temperature, which is naturally cooled to, after 650 DEG C of calcining 6h obtains lithium iron phosphate positive material.
Phosphate compounds are added in alcohols solvent, obtain phosphate ester solution.Preferably, which is first
One of alcohol, ethyl alcohol, propyl alcohol, n-butanol and isopropanol or more than one double solvents, the phosphate compounds general formula
It can be AnP(O)(OH)m, wherein A is carbon oxygen groups corresponding with the alcohol solvent molecules, i.e. methoxyl group, ethyoxyl, the third oxygen
At least one of base, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；Phosphate compounds and alcohols solvent
Mass ratio is 1:5.
Aluminium salt is added in the phosphate ester solution, which is dissolved in the alcohols solvent, and anti-with the phosphate compounds
Homogeneous clear solution should be obtained, reaction temperature is 40 DEG C, and the reaction time is 2 hours；Preferably, aluminium salt is aluminium chloride, nitric acid
One of aluminium, aluminium isopropoxide and aluctyl or more than one.The total additional amount of the alcohol-soluble aluminium salt and alcohols solvent mass ratio
Preferably 1:10.
Addition acidity regulator adjusts the pH value of the homogeneous clear solution to 6-7, and acidity regulator can be ammonium hydroxide, carbon
One of sour hydrogen ammonium, ammonium carbonate, ammonium acetate, pyridine and triethylamine or more than one, the total additional amount of the acidity regulator is pressed
It is that 1:1 weighs to obtain the positive electrode active materials covering liquid according to N:Al molar ratio.
The lithium iron phosphate positive material is uniformly mixed with the positive electrode active materials covering liquid, obtains solid-liquid mixing
Object；And by solidliquid mixture drying and be sintered, which can be room temperature naturally dry or heating, drying, as long as it is mixed to remove this
The solvent in object is closed, the temperature of the heating, drying is preferably 60 DEG C.The sintering carries out in air, before making the cladding
The organic group removal in object is driven, the clad is generated.The sintering temperature is 450 DEG C, and sintering time is 5 hours, obtains anode
Composite material, the anode composite material include positive electrode active materials and the clad for being coated on the surface of positive electrode active material.
Embodiment two
Lithium carbonate, ammonium dihydrogen phosphate, ferrous oxalate are weighed respectively according to the ratio of stoichiometric ratio 1:1:1, are added anhydrous
Ethyl alcohol is carried out after mixing with 500rpm revolving speed ball milling 10h, then obtains ferric lithium phosphate precursor in 90 DEG C of vacuum drying 20h
Powder.
By ferric lithium phosphate precursor obtained in the tube furnace of purity nitrogen atmosphere protection 420 DEG C of heat preservation 6h, be continuously heating to
Room temperature, which is naturally cooled to, after 750 DEG C of calcining 10h obtains lithium iron phosphate positive material.
Phosphate compounds are added in alcohols solvent, obtain phosphate ester solution.The alcohols solvent is isopropanol, the phosphorus
Acid esters compound general formula can be AnP(O)(OH)m, wherein A is carbon oxygen groups corresponding with the alcohol solvent molecules, i.e. methoxy
At least one of base, ethyoxyl, propoxyl group, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；Phosphoric acid ester chemical combination
The mass ratio of object and alcohols solvent is 1:25.
Aluminium salt is added in the phosphate ester solution, which is dissolved in the alcohols solvent, and anti-with the phosphate compounds
Homogeneous clear solution should be obtained, reaction temperature is 80 DEG C, and the reaction time is 5 hours；Preferably, aluminium salt is aluminium chloride, nitric acid
One of aluminium, aluminium isopropoxide and aluctyl or more than one.The total additional amount of the alcohol-soluble aluminium salt and alcohols solvent mass ratio
Preferably 1:20.
Addition acidity regulator adjusts the pH value of the homogeneous clear solution to 6-7, and acidity regulator can be ammonium hydroxide, carbon
One of sour hydrogen ammonium, ammonium carbonate, ammonium acetate, pyridine and triethylamine or more than one, the total additional amount of the acidity regulator is pressed
It is that 6:1 weighs to obtain the positive electrode active materials covering liquid according to N:Al molar ratio.
The lithium iron phosphate positive material is uniformly mixed with the positive electrode active materials covering liquid, obtains solid-liquid mixing
Object；And by solidliquid mixture drying and be sintered, which can be room temperature naturally dry or heating, drying, as long as it is mixed to remove this
The solvent in object is closed, the temperature of the heating, drying is preferably 100 DEG C.The sintering carries out in air, makes the cladding
Organic group removal in predecessor, generates the clad.The sintering temperature is 750 DEG C, and sintering time is 8 hours, is obtained just
Pole composite material, the anode composite material include positive electrode active materials and the clad for being coated on the surface of positive electrode active material.
Comparative example
Commercially available lithium iron phosphate positive material.
Using above-described embodiment one, two and comparative example products therefrom using NMP as solvent, by active material: SP: PVDF
Be configured to slurry that solid content be 70% at=90: 5: 5 is evenly applied on Al foil, and anode is made.Cathode selects diameter 14mm's
Metal lithium sheet, electrolyte selects 1mol LiFP6 (EC:DMC:EMC=1:1:1, v/v), with negative electrode casing-elastic slice-gasket-lithium
Battery is packaged by piece-electrolyte-diaphragm-positive plate-gasket-anode cover sequence, and whole process is all filled with argon
It is completed in the glove box of gas.Electric performance test is carried out at being 25 DEG C in test temperature, after tested the material of the embodiment one and two
Compared with the product of comparative example, first charge-discharge reversible capacity improves 25-28%, and service life is increased to 50% or more.
Claims (2)
1. a kind of preparation method of lithium iron phosphate positive material, this method comprises the following steps:
(1) LiFePO 4 material is prepared
Lithium carbonate, ammonium dihydrogen phosphate, ferrous oxalate are weighed respectively according to the ratio of stoichiometric ratio 1:1:1, and dehydrated alcohol is added
It is carried out after mixing with 400-500rpm revolving speed ball milling 6-10h, then obtains ferric phosphate in 70-90 DEG C of vacuum drying 10-20h
Lithium precursor；
By ferric lithium phosphate precursor obtained in the tube furnace of purity nitrogen atmosphere protection 380-420 DEG C of heat preservation 4-6h, continue to heat up
Room temperature, which is naturally cooled to, after to 650-750 DEG C of calcining 6-10h obtains lithium iron phosphate positive material；
(2) positive electrode active materials covering liquid is prepared
Phosphate compounds are added in alcohols solvent, obtain phosphate ester solution；
Aluminium salt is added in the phosphate ester solution, which is dissolved in the alcohols solvent, and reacts with the phosphate compounds
To homogeneous clear solution, reaction temperature is 40-80 DEG C, and the reaction time is 2-5 hours；
Acidity regulator is added and adjusts the pH value of the homogeneous clear solution to 6-7, acidity regulator be ammonium hydroxide, ammonium hydrogen carbonate,
One or more of ammonium carbonate, ammonium acetate, pyridine and triethylamine, the total additional amount of the acidity regulator are according to N:Al molar ratio
1:1-6:1 weighs to obtain the positive electrode active materials covering liquid；
(3) it coats
The lithium iron phosphate positive material is uniformly mixed with the positive electrode active materials covering liquid, obtains a solidliquid mixture；With
And
It by solidliquid mixture drying and is sintered, which can be room temperature naturally dry or heating, drying, as long as removing the mixing
Solvent in object, the temperature of the heating, drying are 60-100 DEG C, and the sintering carries out in air, makes cladding forerunner
Organic group removal in object, generates the clad, which is 450-750 DEG C, and sintering time is 5-8 hours, obtains
Anode composite material, the anode composite material include positive electrode active materials and the cladding for being coated on the surface of positive electrode active material
Layer；
The alcohols solvent is the solvent of one or more of methanol, ethyl alcohol, propyl alcohol, n-butanol and isopropanol, the phosphoric acid ester
Conjunction object general formula is AnP(O)(OH)m, wherein A is carbon oxygen groups corresponding with the alcohol solvent molecules, i.e. methoxyl group, ethyoxyl, third
At least one of oxygroup, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；Phosphate compounds and alcohols solvent
Mass ratio be 1:5-1:25.
2. the method as described in claim 1, which is characterized in that aluminium salt is in aluminium chloride, aluminum nitrate, aluminium isopropoxide and aluctyl
More than one, the total additional amount of aluminium salt and alcohols solvent mass ratio are 1:10-1:20.
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| CN102447105A (en) * | 2010-10-14 | 2012-05-09 | 清华大学 | Lithium nickel oxide composite material and preparation method thereof and lithium ion battery |
| CN102956895A (en) * | 2012-11-15 | 2013-03-06 | 北大先行科技产业有限公司 | Surface composite coated anode material, preparation method thereof and lithium ion battery |
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| CN102447105A (en) * | 2010-10-14 | 2012-05-09 | 清华大学 | Lithium nickel oxide composite material and preparation method thereof and lithium ion battery |
| CN102956895A (en) * | 2012-11-15 | 2013-03-06 | 北大先行科技产业有限公司 | Surface composite coated anode material, preparation method thereof and lithium ion battery |
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