CN108773839A - A kind of preparation method of high-pressure solid LiFePO4 - Google Patents
A kind of preparation method of high-pressure solid LiFePO4 Download PDFInfo
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- CN108773839A CN108773839A CN201810611876.8A CN201810611876A CN108773839A CN 108773839 A CN108773839 A CN 108773839A CN 201810611876 A CN201810611876 A CN 201810611876A CN 108773839 A CN108773839 A CN 108773839A
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- 239000007787 solid Substances 0.000 title claims abstract description 30
- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 160
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000005245 sintering Methods 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 34
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 34
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 34
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 238000000498 ball milling Methods 0.000 claims abstract description 28
- 238000003801 milling Methods 0.000 claims abstract description 22
- 239000004576 sand Substances 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 18
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 15
- 229940062993 ferrous oxalate Drugs 0.000 claims abstract description 15
- 239000008103 glucose Substances 0.000 claims abstract description 15
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000004806 packaging method and process Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims description 39
- 238000007599 discharging Methods 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 claims description 7
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 8
- 229960001031 glucose Drugs 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical class [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 208000011580 syndromic disease Diseases 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention discloses a kind of preparation method of high-pressure solid LiFePO4.By ferrous oxalate and lithium phosphate according to molar ratio 1:1 mixing, by adding water for ball milling and sand milling, is spray-dried, obtained dry powder through oversintering, obtains primary sintered material under an inert atmosphere；Ferric phosphate and glucose is added in primary sintered material, and the ferric phosphate of addition and the molar ratio of the lithium phosphate of step (1) addition are 2:1, then by adding water for ball milling and sand milling, obtain the material that grain size is 314nm, material is spray-dried to obtain moisture less than the dry powder that 2%, grain size is 1.5 microns, obtained dry powder is under an inert atmosphere through oversintering, and obtained dry powder is under an inert atmosphere through oversintering, obtain double sintering material, it is crushed, sieved in constant temperature and humidity room, except after iron, being filled with nitrogen, then vacuumize packaging again.The method of the present invention is simple, at low cost, and obtained LiFePO4 compacted density is high, good electrical property.
Description
Technical field
The present invention relates to a kind of preparation methods of high-pressure solid LiFePO4, belong to anode material of lithium battery technical field.
Background technology
LiFePO4 is a kind of new type lithium ion battery electrode material.Its main feature is that discharge capacity is big, and it is cheap, it is nontoxic
Property, do not cause environmental pollution.Just competitively realize industrialization production in countries in the world.But its tap density is low, influences capacitance.It is main
The production method wanted is high temperature solid phase synthesis, and product index is more stable.The performance of lithium ion battery depends primarily on positive and negative
Pole material, LiFePO4 are the things just occurred in recent years as the positive electrode of lithium ion battery, and domestic-developed goes out large capacity phosphorus
Sour lithium iron battery is in July, 2005.Its security performance with cycle life be other materials can not compared with, these are also exactly dynamic
The most important technical indicator of power battery.The 1C charge-discharge cycle service life is up to 2000 times.Single battery overcharged voltage 30V does not burn, and punctures
It does not explode.Lithium iron phosphate positive material makes high capacity lithium ion battery and is more easy to be used in series.To meet the frequent charge and discharge of electric vehicle
The needs of electricity.Have many advantages, such as it is nontoxic, pollution-free, have a safety feature, raw material sources are extensive, cheap, long lifespan is new
The ideal positive electrode of generation lithium ion battery.
But the adjustment with country to new-energy automobile subsidy policy, the requirement to LiFePO 4 material is higher and higher,
Requirement especially to the compacted density of LiFePO4 is higher and higher, and the > 2.3g/mL from before rise 2.35g/mL till now,
And > 2.4g/mL or higher can be promoted later, the requirement simultaneously for the gram volume of 0.1C is maintained above 156mAh.
Invention content
In view of this, the present invention provides a kind of preparation method of high-pressure solid LiFePO4, method is simple, at low cost, and
Obtained LiFePO4 compacted density is high, good electrical property, is prepared with ferric phosphate by the LiFePO4 prepared with ferrous oxalate
LiFePO4 it is compound, combine the cycle of LiFePO4 and the advantage of low temperature performance well and phosphoric acid of ferrous oxalate preparation
The good advantage of iron standby electrochemical performances of lithium iron phosphate, while avoiding ferrous oxalate and prepare LiFePO4 and releasing ammonia
Disadvantage, the feature of environmental protection is good, and avoids using raw materials such as lithium carbonates, reduces cost, and by double sintering, it is close to improve compacting
Degree does not influence electrical property further through compound, and finally obtained product compacted density is more than 2.45g/mL, and 0.1C is for the first time
Discharge capacity is more than 157mAh/g, and the capacity attenuation rate that 0.5C recycles 500 times is less than 15%.
The present invention solves above-mentioned technical problem by following technological means：
A kind of preparation method of high-pressure solid LiFePO4, is following steps：
(1) by ferrous oxalate and lithium phosphate according to molar ratio 1:1 mixing, by adding water for ball milling and sand milling, obtaining grain size is
Material is spray-dried to obtain moisture less than the dry powder that 2%, grain size is 1-3 microns, is obtained by the material of 450-480nm
Dry powder obtains primary sintered material under an inert atmosphere through oversintering, and sintering total time is 12-15 hour, is sintered and is divided into three sections, the
One section is warming-up section, and material is 3-5 hours in the warming-up section residence time, and second segment is soaking zone, and material is when soaking zone stops
Between be 5-8 hour, the temperature of soaking zone is 720-750 DEG C, and third section is temperature descending section, and material is 2-4 in the temperature descending section residence time
Hour, it is cooled to 80 DEG C of dischargings of temperature of charge <；
(2) ferric phosphate and glucose, ferric phosphate and the step (1) of addition is added in the primary sintered material for obtaining step (1)
The molar ratio of the lithium phosphate of addition is 2:1, then through and adding water for ball milling and sand milling, obtains the material that grain size is 300-320nm, it will
Material is spray-dried to obtain moisture less than the dry powder that 2%, grain size is 1-3 microns, and obtained dry powder passes through under an inert atmosphere
Oversintering, obtained dry powder through oversintering, obtain double sintering material under an inert atmosphere, and sintering total time is 21-23 hours, is burnt
Knot is divided into three sections, and first segment is warming-up section, and material is 6-8 hours in the warming-up section residence time, and second segment is soaking zone, and material exists
The soaking zone residence time is 10-12 hours, and the temperature of soaking zone is 760-770 DEG C, and third section is temperature descending section, and material is in temperature descending section
Residence time is 3-5 hours, is cooled to 50 DEG C of dischargings of temperature of charge <；
(3) the cooling material for obtaining step (2) is crushed in constant temperature and humidity room, is sieved, except after iron, being filled with nitrogen
Then gas vacuumizes packaging again.
In the step (1) by ball milling and after being sanded, the solid content of material is 40-41%, spray drying into wind-warm syndrome
Degree is 180-200 DEG C, and residence time of the material in spray dryer is 6-10S, and the inert atmosphere is nitrogen, in nitrogen
Oxygen content is less than 5ppm, is passed through inert atmosphere and so that the furnace pressure in sintering furnace is 1.05-1.1 atmospheric pressure, material is in saggar
Interior charging thickness is 10-12cm.
The weight for the glucose being added in the step (2) is the 14-15% of ferric phosphate weight, passes through ball in step (2)
After mill and sand milling, the solid content of material is 30-35%, and the inlet air temperature of spray drying is 180-200 DEG C, and material is being spray-dried
Residence time in machine is 6-10S, and the inert atmosphere is nitrogen, and the oxygen content in nitrogen is less than 5ppm, is passed through indifferent gas
Atmosphere so that the furnace pressure in sintering furnace is 1.05-1.1 atmospheric pressure, and charging thickness of the material in saggar is 5-8cm.
Temperature is 10-15 DEG C in constant temperature and humidity room in the step (3), and relative humidity≤10% is crushed to the grain of material
Diameter is 1-1.5 micron, and when screening crosses 200 mesh and sieves.
The purity of step (1) the mesoxalic acid ferrous iron is more than 99.5%, and granularity is 2-3 microns, BET 6-8m2/ g, mistake
150 mesh sieve, and tap density is more than 1.5g/mL, and impurity content is less than 100ppm.
The iron phosphorus ratio of ferric phosphate is 0.98-0.985 in the step (2), and granularity is 1-3 microns, tap density 0.6-
0.7g/mL, specific surface area 7-10m2/g。
This patent first passes through ferrous oxalate and is carried out once with lithium phosphate using lithium phosphate, ferrous oxalate and ferric phosphate as raw material
Sintering, then ferric phosphate is added, remaining lithium is reacted completely, by the compound and double sintering of the two, improves compacted density,
Phosphoric acid prepared by the cycle of LiFePO4 and the advantage of low temperature performance well and ferric phosphate prepared in combination with ferrous oxalate
The good advantage of iron lithium electrochemical performance, while avoiding ferrous oxalate and preparing the shortcomings that LiFePO4 releases ammonia, the feature of environmental protection
It is good, and avoid using raw materials such as lithium carbonates, cost is reduced, and by double sintering, improve compacted density, further through multiple
It closes, electrical property is not influenced, finally obtained product compacted density is more than 2.45g/mL, and discharge capacity is more than 0.1C for the first time
The capacity attenuation rate that 157mAh/g, 0.5C recycle 500 times is less than 15%.
The beneficial effects of the invention are as follows：Method is simple, at low cost, and obtained LiFePO4 compacted density is high, electrical property
It is good.
Specific implementation mode
Below with reference to specific embodiment, the present invention is described in detail, a kind of high-pressure solid LiFePO4 of the present embodiment
Preparation method, be following steps：
(1) by ferrous oxalate and lithium phosphate according to molar ratio 1:1 mixing, by adding water for ball milling and sand milling, obtaining grain size is
Material is spray-dried to obtain moisture less than the dry powder that 2%, grain size is 1-3 microns, is obtained by the material of 450-480nm
Dry powder obtains primary sintered material under an inert atmosphere through oversintering, and sintering total time is 12-15 hour, is sintered and is divided into three sections, the
One section is warming-up section, and material is 3-5 hours in the warming-up section residence time, and second segment is soaking zone, and material is when soaking zone stops
Between be 5-8 hour, the temperature of soaking zone is 720-750 DEG C, and third section is temperature descending section, and material is 2-4 in the temperature descending section residence time
Hour, it is cooled to 80 DEG C of dischargings of temperature of charge <；
(2) ferric phosphate and glucose, ferric phosphate and the step (1) of addition is added in the primary sintered material for obtaining step (1)
The molar ratio of the lithium phosphate of addition is 2:1, then through and adding water for ball milling and sand milling, obtains the material that grain size is 300-320nm, it will
Material is spray-dried to obtain moisture less than the dry powder that 2%, grain size is 1-3 microns, and obtained dry powder passes through under an inert atmosphere
Oversintering, obtained dry powder through oversintering, obtain double sintering material under an inert atmosphere, and sintering total time is 21-23 hours, is burnt
Knot is divided into three sections, and first segment is warming-up section, and material is 6-8 hours in the warming-up section residence time, and second segment is soaking zone, and material exists
The soaking zone residence time is 10-12 hours, and the temperature of soaking zone is 760-770 DEG C, and third section is temperature descending section, and material is in temperature descending section
Residence time is 3-5 hours, is cooled to 50 DEG C of dischargings of temperature of charge <；
(3) the cooling material for obtaining step (2) is crushed in constant temperature and humidity room, is sieved, except after iron, being filled with nitrogen
Then gas vacuumizes packaging again.
In the step (1) by ball milling and after being sanded, the solid content of material is 40-41%, spray drying into wind-warm syndrome
Degree is 180-200 DEG C, and residence time of the material in spray dryer is 6-10S, and the inert atmosphere is nitrogen, in nitrogen
Oxygen content is less than 5ppm, is passed through inert atmosphere and so that the furnace pressure in sintering furnace is 1.05-1.1 atmospheric pressure, material is in saggar
Interior charging thickness is 10-12cm.
The weight for the glucose being added in the step (2) is the 14-15% of ferric phosphate weight, passes through ball in step (2)
After mill and sand milling, the solid content of material is 30-35%, and the inlet air temperature of spray drying is 180-200 DEG C, and material is being spray-dried
Residence time in machine is 6-10S, and the inert atmosphere is nitrogen, and the oxygen content in nitrogen is less than 5ppm, is passed through indifferent gas
Atmosphere so that the furnace pressure in sintering furnace is 1.05-1.1 atmospheric pressure, and charging thickness of the material in saggar is 5-8cm.
Temperature is 10-15 DEG C in constant temperature and humidity room in the step (3), and relative humidity≤10% is crushed to the grain of material
Diameter is 1-1.5 micron, and when screening crosses 200 mesh and sieves.
The purity of step (1) the mesoxalic acid ferrous iron is more than 99.5%, and granularity is 2-3 microns, BET 6-8m2/ g, mistake
150 mesh sieve, and tap density is more than 1.5g/mL, and impurity content is less than 100ppm.
The iron phosphorus ratio of ferric phosphate is 0.98-0.985 in the step (2), and granularity is 1-3 microns, tap density 0.6-
0.7g/mL, specific surface area 7-10m2/g。
Embodiment 1
A kind of preparation method of high-pressure solid LiFePO4, is following steps：
(1) by ferrous oxalate and lithium phosphate according to molar ratio 1:1 mixing, by adding water for ball milling and sand milling, obtaining grain size is
Material is spray-dried to obtain moisture less than 2%, grain size as 2.1 microns of dry powder, obtained dry powder by the material of 465nm
Under an inert atmosphere through oversintering, primary sintered material is obtained, sintering total time is 14 hours, and sintering is divided into three sections, and first segment is
Warming-up section, material are 4 hours in the warming-up section residence time, and second segment is soaking zone, and material is 8 small in the soaking zone residence time
When, the temperature of soaking zone is 745 DEG C, and third section is temperature descending section, and material is 2 hours in the temperature descending section residence time, is cooled to material
80 DEG C of dischargings of temperature <；
(2) ferric phosphate and glucose, ferric phosphate and the step (1) of addition is added in the primary sintered material for obtaining step (1)
The molar ratio of the lithium phosphate of addition is 2:1, then by adding water for ball milling and sand milling, the material that grain size is 314nm is obtained, by material
It is spray-dried to obtain moisture less than the dry powder that 2%, grain size is 1.5 microns, obtained dry powder is under an inert atmosphere through burning
Knot, obtained dry powder through oversintering, obtain double sintering material under an inert atmosphere, and sintering total time is 22 hours, and sintering is divided into
Three sections, first segment is warming-up section, and material is 7 hours in the warming-up section residence time, and second segment is soaking zone, and material stops in soaking zone
It is 11 hours to stay the time, and the temperature of soaking zone is 766 DEG C, and third section is temperature descending section, and material is 4 small in the temperature descending section residence time
When, it is cooled to 50 DEG C of dischargings of temperature of charge <；
(3) the cooling material for obtaining step (2) is crushed in constant temperature and humidity room, is sieved, except after iron, being filled with nitrogen
Then gas vacuumizes packaging again.
In the step (1) by ball milling and after being sanded, the solid content of material is 40.5%, the inlet air temperature of spray drying
It it is 195 DEG C, residence time of the material in spray dryer is 9S, and the inert atmosphere is nitrogen, the oxygen content in nitrogen
Less than 5ppm, it is passed through inert atmosphere and so that the furnace pressure in sintering furnace is 1.08 atmospheric pressure, charging thickness of the material in saggar
For 11cm.
The weight for the glucose being added in the step (2) is the 14.5% of ferric phosphate weight, passes through ball milling in step (2)
After sand milling, the solid content of material is 31%, and the inlet air temperature of spray drying is 188 DEG C, and material stops in spray dryer
It is 9S to stay the time, and the inert atmosphere is nitrogen, and the oxygen content in nitrogen is less than 5ppm, is passed through inert atmosphere and makes sintering furnace
Interior furnace pressure is 1.09 atmospheric pressure, and charging thickness of the material in saggar is 7cm.
Temperature is 13 DEG C in constant temperature and humidity room in the step (3), relative humidity≤10%, and the grain size for being crushed to material is
1.25 microns, when screening, crosses 200 mesh sieve.
The purity of step (1) the mesoxalic acid ferrous iron is more than 99.5%, and granularity is 2.1 microns, BET 7.2m2/ g, mistake
150 mesh sieve, and tap density is more than 1.5g/mL, and impurity content is less than 100ppm.
The iron phosphorus ratio of ferric phosphate is 0.981 in the step (2), and granularity is 1.5 microns, tap density 0.66g/mL,
Specific surface area is 9.2m2/g。
Finally obtained product index is as follows：
Embodiment 2
A kind of preparation method of high-pressure solid LiFePO4, is following steps：
(1) by ferrous oxalate and lithium phosphate according to molar ratio 1:1 mixing, by adding water for ball milling and sand milling, obtaining grain size is
Material is spray-dried to obtain moisture less than 2%, grain size as 1.9 microns of dry powder, obtained dry powder by the material of 465nm
Under an inert atmosphere through oversintering, primary sintered material is obtained, sintering total time is 13 hours, and sintering is divided into three sections, and first segment is
Warming-up section, material are 3 hours in the warming-up section residence time, and second segment is soaking zone, and material is 6 small in the soaking zone residence time
When, the temperature of soaking zone is 745 DEG C, and third section is temperature descending section, and material is 4 hours in the temperature descending section residence time, is cooled to material
80 DEG C of dischargings of temperature <；
(2) ferric phosphate and glucose, ferric phosphate and the step (1) of addition is added in the primary sintered material for obtaining step (1)
The molar ratio of the lithium phosphate of addition is 2:1, then by adding water for ball milling and sand milling, the material that grain size is 315nm is obtained, by material
It is spray-dried to obtain moisture less than the dry powder that 2%, grain size is 2.5 microns, obtained dry powder is under an inert atmosphere through burning
Knot, obtained dry powder through oversintering, obtain double sintering material under an inert atmosphere, and sintering total time is 22 hours, and sintering is divided into
Three sections, first segment is warming-up section, and material is 7 hours in the warming-up section residence time, and second segment is soaking zone, and material stops in soaking zone
It is 12 hours to stay the time, and the temperature of soaking zone is 760 DEG C, and third section is temperature descending section, and material is 3 small in the temperature descending section residence time
When, it is cooled to 50 DEG C of dischargings of temperature of charge <；
(3) the cooling material for obtaining step (2) is crushed in constant temperature and humidity room, is sieved, except after iron, being filled with nitrogen
Then gas vacuumizes packaging again.
In the step (1) by ball milling and after being sanded, the solid content of material is 40.3%, the inlet air temperature of spray drying
It it is 189 DEG C, residence time of the material in spray dryer is 8S, and the inert atmosphere is nitrogen, the oxygen content in nitrogen
Less than 5ppm, it is passed through inert atmosphere and so that the furnace pressure in sintering furnace is 1.06 atmospheric pressure, charging thickness of the material in saggar
For 11.5cm.
The weight for the glucose being added in the step (2) is the 14.2% of ferric phosphate weight, passes through ball milling in step (2)
After sand milling, the solid content of material is 33%, and the inlet air temperature of spray drying is 185 DEG C, and material stops in spray dryer
It is 8S to stay the time, and the inert atmosphere is nitrogen, and the oxygen content in nitrogen is less than 5ppm, is passed through inert atmosphere and makes sintering furnace
Interior furnace pressure is 1.08 atmospheric pressure, and charging thickness of the material in saggar is 7.5cm.
Temperature is 13 DEG C in constant temperature and humidity room in the step (3), relative humidity≤10%, and the grain size for being crushed to material is
1.35 microns, when screening, crosses 200 mesh sieve.
The purity of step (1) the mesoxalic acid ferrous iron is more than 99.5%, and granularity is 2.6 microns, BET 7.2m2/ g, mistake
150 mesh sieve, and tap density is more than 1.5g/mL, and impurity content is less than 100ppm.
The iron phosphorus ratio of ferric phosphate is 0.984 in the step (2), and granularity is 1.3 microns, tap density 0.66g/mL,
Specific surface area is 9.5m2/g。
Finally obtained product index is as follows：
Embodiment 3
A kind of preparation method of high-pressure solid LiFePO4, is following steps：
(1) by ferrous oxalate and lithium phosphate according to molar ratio 1:1 mixing, by adding water for ball milling and sand milling, obtaining grain size is
Material is spray-dried to obtain moisture less than 2%, grain size as 2.8 microns of dry powder, obtained dry powder by the material of 460nm
Under an inert atmosphere through oversintering, primary sintered material is obtained, sintering total time is 13 hours, and sintering is divided into three sections, and first segment is
Warming-up section, material are 4 hours in the warming-up section residence time, and second segment is soaking zone, and material is 6 small in the soaking zone residence time
When, the temperature of soaking zone is 725 DEG C, and third section is temperature descending section, and material is 3 hours in the temperature descending section residence time, is cooled to material
80 DEG C of dischargings of temperature <；
(2) ferric phosphate and glucose, ferric phosphate and the step (1) of addition is added in the primary sintered material for obtaining step (1)
The molar ratio of the lithium phosphate of addition is 2:1, then by adding water for ball milling and sand milling, the material that grain size is 305nm is obtained, by material
It is spray-dried to obtain moisture less than the dry powder that 2%, grain size is 1.9 microns, obtained dry powder is under an inert atmosphere through burning
Knot, obtained dry powder through oversintering, obtain double sintering material under an inert atmosphere, and sintering total time is 21.5 hours, sintering point
It it is three sections, first segment is warming-up section, and material is 7.5 hours in the warming-up section residence time, and second segment is soaking zone, and material is being kept the temperature
The section residence time is 11 hours, and the temperature of soaking zone is 766 DEG C, and third section is temperature descending section, and material is 3 in the temperature descending section residence time
Hour, it is cooled to 50 DEG C of dischargings of temperature of charge <；
(3) the cooling material for obtaining step (2) is crushed in constant temperature and humidity room, is sieved, except after iron, being filled with nitrogen
Then gas vacuumizes packaging again.
In the step (1) by ball milling and after being sanded, the solid content of material is 40.7%, the inlet air temperature of spray drying
It it is 189 DEG C, residence time of the material in spray dryer is 9S, and the inert atmosphere is nitrogen, the oxygen content in nitrogen
Less than 5ppm, it is passed through inert atmosphere and so that the furnace pressure in sintering furnace is 1.09 atmospheric pressure, charging thickness of the material in saggar
For 11.5cm.
The weight for the glucose being added in the step (2) is the 14.9% of ferric phosphate weight, passes through ball milling in step (2)
After sand milling, the solid content of material is 33%, and the inlet air temperature of spray drying is 195 DEG C, and material stops in spray dryer
It is 8S to stay the time, and the inert atmosphere is nitrogen, and the oxygen content in nitrogen is less than 5ppm, is passed through inert atmosphere and makes sintering furnace
Interior furnace pressure is 1.09 atmospheric pressure, and charging thickness of the material in saggar is 8cm.
Temperature is 13 DEG C in constant temperature and humidity room in the step (3), relative humidity≤10%, and the grain size for being crushed to material is
1.2 microns, when screening, crosses 200 mesh sieve.
The purity of step (1) the mesoxalic acid ferrous iron is more than 99.5%, and granularity is 2.8 microns, BET 7.2m2/ g, mistake
150 mesh sieve, and tap density is more than 1.5g/mL, and impurity content is less than 100ppm.
The iron phosphorus ratio of ferric phosphate is 0.982 in the step (2), and granularity is 1.8 microns, tap density 0.68g/mL,
Specific surface area is 9.5m2/g。
Finally obtained product index is as follows：
Embodiment 4
A kind of preparation method of high-pressure solid LiFePO4, is following steps：
(1) by ferrous oxalate and lithium phosphate according to molar ratio 1:1 mixing, by adding water for ball milling and sand milling, obtaining grain size is
Material is spray-dried to obtain moisture less than 2%, grain size as 1.9 microns of dry powder, obtained dry powder by the material of 455nm
Under an inert atmosphere through oversintering, primary sintered material is obtained, sintering total time is 14 hours, and sintering is divided into three sections, and first segment is
Warming-up section, material are 4.5 hours in the warming-up section residence time, and second segment is soaking zone, and material is 7.5 in the soaking zone residence time
Hour, the temperature of soaking zone is 748 DEG C, and third section is temperature descending section, and material is 2 hours in the temperature descending section residence time, is cooled to object
80 DEG C of dischargings of material temperature degree <；
(2) ferric phosphate and glucose, ferric phosphate and the step (1) of addition is added in the primary sintered material for obtaining step (1)
The molar ratio of the lithium phosphate of addition is 2:1, then by adding water for ball milling and sand milling, the material that grain size is 315nm is obtained, by material
It is spray-dried to obtain moisture less than the dry powder that 2%, grain size is 1.8 microns, obtained dry powder is under an inert atmosphere through burning
Knot, obtained dry powder through oversintering, obtain double sintering material under an inert atmosphere, and sintering total time is 22.5 hours, sintering point
It it is three sections, first segment is warming-up section, and material is 7.5 hours in the warming-up section residence time, and second segment is soaking zone, and material is being kept the temperature
The section residence time is 11.5 hours, and the temperature of soaking zone is 769 DEG C, and third section is temperature descending section, and material is in the temperature descending section residence time
It is 3.5 hours, is cooled to 50 DEG C of dischargings of temperature of charge <；
(3) the cooling material for obtaining step (2) is crushed in constant temperature and humidity room, is sieved, except after iron, being filled with nitrogen
Then gas vacuumizes packaging again.
In the step (1) by ball milling and after being sanded, the solid content of material is 40.5%, the inlet air temperature of spray drying
It it is 189 DEG C, residence time of the material in spray dryer is 9S, and the inert atmosphere is nitrogen, the oxygen content in nitrogen
Less than 5ppm, it is passed through inert atmosphere and so that the furnace pressure in sintering furnace is 1.085 atmospheric pressure, charging thickness of the material in saggar
For 12cm.
The weight for the glucose being added in the step (2) is the 14.1% of ferric phosphate weight, passes through ball milling in step (2)
After sand milling, the solid content of material is 33%, and the inlet air temperature of spray drying is 189 DEG C, and material stops in spray dryer
It is 9S to stay the time, and the inert atmosphere is nitrogen, and the oxygen content in nitrogen is less than 5ppm, is passed through inert atmosphere and makes sintering furnace
Interior furnace pressure is 1.06 atmospheric pressure, and charging thickness of the material in saggar is 7.2cm.
Temperature is 14 DEG C in constant temperature and humidity room in the step (3), relative humidity≤10%, and the grain size for being crushed to material is
1.45 microns, when screening, crosses 200 mesh sieve.
The purity of step (1) the mesoxalic acid ferrous iron is more than 99.5%, and granularity is 2.8 microns, BET 7.8m2/ g, mistake
150 mesh sieve, and tap density is more than 1.5g/mL, and impurity content is less than 100ppm.
The iron phosphorus ratio of ferric phosphate is 0.983 in the step (2), and granularity is 2.5 microns, tap density 0.67g/mL,
Specific surface area is 8.2m2/g。
Finally obtained product index is as follows：
Finally illustrate, the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to compared with
Good embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the right of invention.
Claims (6)
1. a kind of preparation method of high-pressure solid LiFePO4, which is characterized in that be following steps：
(1) by ferrous oxalate and lithium phosphate according to molar ratio 1:1 mixing, by adding water for ball milling and sand milling, it is 450- to obtain grain size
Material is spray-dried to obtain moisture less than 2%, grain size as 1-3 microns of dry powder, obtained dry powder by the material of 480nm
Under an inert atmosphere through oversintering, primary sintered material is obtained, sintering total time is 12-15 hours, and sintering is divided into three sections, first segment
For warming-up section, material is 3-5 hours in the warming-up section residence time, and second segment is soaking zone, and material is in the soaking zone residence time
5-8 hours, the temperature of soaking zone was 720-750 DEG C, and third section is temperature descending section, and material is 2-4 hours in the temperature descending section residence time,
It is cooled to 80 DEG C of dischargings of temperature of charge <；
(2) ferric phosphate and glucose is added in the primary sintered material for obtaining step (1), and ferric phosphate and the step (1) of addition are added
Lithium phosphate molar ratio be 2:1, then by adding water for ball milling and sand milling, the material that grain size is 300-320nm is obtained, by material
It is spray-dried to obtain moisture less than the dry powder that 2%, grain size is 1-3 microns, obtained dry powder is under an inert atmosphere through burning
Knot, obtained dry powder through oversintering, obtain double sintering material under an inert atmosphere, and sintering total time is 21-23 hours, sintering point
It it is three sections, first segment is warming-up section, and material is 6-8 hours in the warming-up section residence time, and second segment is soaking zone, and material is being kept the temperature
The section residence time is 10-12 hours, and the temperature of soaking zone is 760-770 DEG C, and third section is temperature descending section, and material is stopped in temperature descending section
Time is 3-5 hours, is cooled to 50 DEG C of dischargings of temperature of charge <；
(3) the cooling material for obtaining step (2) is crushed in constant temperature and humidity room, is sieved, except after iron, being filled with nitrogen, so
Vacuumize packaging again afterwards.
2. a kind of preparation method of high-pressure solid LiFePO4 according to claim 1, it is characterised in that：The step (1)
Middle by ball milling and after being sanded, the solid content of material is 40-41%, and the inlet air temperature of spray drying is 180-200 DEG C, and material exists
Residence time in spray dryer is 6-10S, and the inert atmosphere is nitrogen, and the oxygen content in nitrogen is less than 5ppm, leads to
Enter inert atmosphere and so that the furnace pressure in sintering furnace is 1.05-1.1 atmospheric pressure, charging thickness of the material in saggar is 10-
12cm。
3. a kind of preparation method of high-pressure solid LiFePO4 according to claim 1, it is characterised in that：The step (2)
The weight of the glucose of middle addition is the 14-15% of ferric phosphate weight, and in step (2) by ball milling and after being sanded, material is consolidated
Content is 30-35%, and the inlet air temperature of spray drying is 180-200 DEG C, and residence time of the material in spray dryer is 6-
10S, the inert atmosphere are nitrogen, and the oxygen content in nitrogen is less than 5ppm, are passed through inert atmosphere and make stove in sintering furnace
Pressure is 1.05-1.1 atmospheric pressure, and charging thickness of the material in saggar is 5-8cm.
4. a kind of preparation method of high-pressure solid LiFePO4 according to claim 1, it is characterised in that：The step (3)
Temperature is 10-15 DEG C in middle constant temperature and humidity room, relative humidity≤10%, and the grain size for being crushed to material is 1-1.5 microns, when screening
Cross 200 mesh sieve.
5. a kind of preparation method of high-pressure solid LiFePO4 according to claim 1, it is characterised in that：The step (1)
The purity of mesoxalic acid ferrous iron is more than 99.5%, and granularity is 2-3 microns, BET 6-8m2/ g, crosses 150 mesh sieve, and tap density is big
In 1.5g/mL, impurity content is less than 100ppm.
6. a kind of preparation method of high-pressure solid LiFePO4 according to claim 1, it is characterised in that：The step (2)
The iron phosphorus ratio of middle ferric phosphate is 0.98-0.985, and granularity is 1-3 microns, tap density 0.6-0.7g/mL, specific surface area 7-
10m2/g。
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| CN109650366A (en) * | 2018-11-22 | 2019-04-19 | 湖北融通高科先进材料有限公司 | A kind of LiFePO4 and preparation method thereof |
| CN109921003A (en) * | 2019-04-18 | 2019-06-21 | 王东升 | A kind of preparation method of high-pressure solid LiFePO4 |
| CN111392705A (en) * | 2020-02-25 | 2020-07-10 | 东莞东阳光科研发有限公司 | Preparation method of high-compaction lithium iron phosphate |
| CN113745503A (en) * | 2021-08-04 | 2021-12-03 | 北京泰丰先行新能源科技有限公司 | Preparation method of high-compaction lithium iron phosphate cathode material |
| CN114314547A (en) * | 2021-12-23 | 2022-04-12 | 山东精工电子科技有限公司 | High-compaction lithium iron phosphate material, sintering method and preparation method |
| CN117088352A (en) * | 2023-10-20 | 2023-11-21 | 宁德时代新能源科技股份有限公司 | Preparation method of lithium iron phosphate, positive electrode active material, positive electrode plate, battery and electricity utilization device |
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