CN207361793U - A kind of lithium iron phosphate positive material preparation facilities - Google Patents
A kind of lithium iron phosphate positive material preparation facilities Download PDFInfo
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- CN207361793U CN207361793U CN201721104655.9U CN201721104655U CN207361793U CN 207361793 U CN207361793 U CN 207361793U CN 201721104655 U CN201721104655 U CN 201721104655U CN 207361793 U CN207361793 U CN 207361793U
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 12
- 239000002994 raw material Substances 0.000 claims abstract description 54
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 41
- 238000012432 intermediate storage Methods 0.000 claims description 15
- 238000011084 recovery Methods 0.000 claims description 14
- 125000003003 spiro group Chemical group 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000013459 approach Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 68
- 238000000034 method Methods 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 20
- 230000005540 biological transmission Effects 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000002440 industrial waste Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000005955 Ferric phosphate Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 229940032958 ferric phosphate Drugs 0.000 description 5
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 5
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910000904 FeC2O4 Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000003836 solid-state method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- OQPHEVHDBFEJRQ-UHFFFAOYSA-N [Li].P(O)(O)(O)=O Chemical compound [Li].P(O)(O)(O)=O OQPHEVHDBFEJRQ-UHFFFAOYSA-N 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910016153 LiMn0.9Fe0.1PO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of lithium iron phosphate positive material preparation facilities, including material homogenizer part, pyroreaction cooling segment and product homogenizing part, pyroreaction cooling segment include screw reactor, screw reactor connection cooling tower.The present apparatus is using continuous high temperature solid phase method production LiFePO4, and the material continuously conveyed in screw reactor improves heat utilization rate, and compares traditional approach, and raw material mixing uniformity is good, and material reaction is uniform；The raw material of nanosizing homogenizing improves the efficiency for charge-discharge of positive electrode and the stability present apparatus replaces traditional intermittent heating equipment using screw reactor（Such as kiln）, energy consumption is reduced, and reaction stability is good.
Description
Technical field
Lithium iron phosphate positive material preparing technical field is the utility model is related to, more particularly, to a kind of iron phosphate lithium positive pole
Material preparation facilities.
Background technology
In recent years, as progressively attention of the people to environmental issue, requirement of the country to environmental protection are continuously improved, new energy vapour
Car and energy storage market develop rapidly, and the high security, high uniformity, high qualification rate and low manufacture cost to battery propose higher
Requirement.As the positive electrode of lithium ion battery, cobalt acid lithium, LiMn2O4 and its derivative are own to have obtained business through different degrees of
Industry.Certainly, for conventional lithium ion battery positive electrode the defects of, people are endeavouring to study continuous improved performance always, but
It is, for electric automobile and high load battery, the utilization rate of battery, the price of positive electrode and the energy of rupture to environment
Power is all very important factor.Therefore, as most promising anode material for lithium-ion batteries, LiFePO4 is due to tool
There is the features such as height ratio capacity, cycle performance are good, security is good, of low cost, pollution-free, attracted a large amount of scholars and industry circle
Concern, and the important kind of anode material for lithium-ion batteries of new generation.
LiFePO4It is rhombic system for olivine-type structure, belongs to Pbmn space groups, Fe and Li forms FeO6And LiO6Eight
Face body, p-shaped is into PO4Tetrahedron.The Li+ parallel with c-axis for continuous linear chain, two-dimensional diffusion can be formed along c-axis and be moved,
Freely deviate from or embedded.Theoretical capacity is 170mAh/g, and actual capacity only has 81% of theoretical capacity or so.With price
Cheap, the advantages that chemical property is good, environmentally friendly pollution-free.
And research of most of researchers to LiFePO4 is concentrated mainly on three aspects：
1. in order to improve the measure that the electric conductivity of LiFePO4 is taken：Mainly there are carbon coating and metal ion mixing.
2. in order to improve the diffusion velocity of lithium ion, so as to change the measure that charging rate is taken：Need to control particle
Particle diameter.
3. for the measure for controlling purity to be done：Need to add inert gas shielding during the reaction, controlling reaction temperature,
Relatively low reaction temperature not only makes that finished product grain size is small, and ferric iron content is low, and avoidable formation.
The preparation method of lithium iron phosphate positive material usually has two kinds of solid phase method and liquid phase method, since liquid phase method can cause greatly
The industrial wastewater of amount, so solid phase method is most common industrialized method.Solid phase method can be divided into high temperature solid-state method, carbon heat also again
A variety of different methods such as former method and iron oxide red method, since high temperature solid-state method has, cost of material is low, and the advantage such as easy to operation, is very
The selection of more factories.Traditional high temperature solid-state method technics comparing falls behind, including：Mixing raw materials --- raw material grinding --- roast
Burn --- middle product grinding --- screening --- carbon coating --- roasting --- finished product grinding --- finished product screening --- product etc.
Technological process.
In above-mentioned technique, mixing raw materials and homogenizing generally be high-speed mixer, high-speed mixer has its advantage, but
It is that intermittent operation be easy to cause unstable between batch and with a batch of non-uniformity.Raw material mixing is uneven to be caused
React uneven, product mix is uneven to cause product chemical property poor.And chemical property is to weigh positive electrode quality
A critically important index.
The roasting various forms of resistance furnaces such as equipment such as roller kilns, pushed bat kiln, rotary furnace.Roaster：1) hot wind is passed through
Heat transfer, heat transfer are washed one's face and rinsed one's mouth only 20 kilocalories/m3.h. DEG C, and the thermal efficiency is extremely low, and under normal circumstances only 50%, therefore high energy consumption；2) invest
Greatly, producing 5000 tons of LiFePO4s per year at least needs 4 heating furnace production lines, invests more than 30,000,000 yuan；3) protect gas dosage big,
Positive electrode does not have immixture on pallet in stove, the uniformity of material is produced a very large impact, so as to influence its electrification
Learn performance and the specific capacity of final products；4) since gas production is big, the compacted density of material can not ensure, influence making for product
With performance, substantial amounts of gas can not be recycled, is directly discharged in air, cause the pollution of air.
Grinding is generally using equipment such as airflow milling, ball mill, nanometer sand mills；And abradant equipment crushing knife will be used
Zirconium or zirconium oxide, will also use zirconium pearl during crushing, overall price is high.Particle diameter after ball milling is 2 μm or so.And phosphorus
The sour elongated 6.63nm of iron lithium average grain diameter, and the raw material of particle diameter 2000nm is difficult uniformly to mix, so using solid phase method, raw material
Particle diameter is bigger, and the actual capacity of the LiFePO 4 material of synthesis is lower.The problem of ball mill processing product brings maximum is exactly to produce
Product particle diameter distribution is wide, and a big chunk product causes the yield rate of product low because particle diameter is improper is just discarded, cost into
The increase of one step.
Screening is general to use vibrating screen, on vibrating screen the product of remaining last batch be cause product it is non-uniform another
Defect.
It is varied in terms of the species of LiFePO4 raw material.Liu Xu is identical to use FeC2O4·2H2O、 Fe2O3、FeCl3Deng
Raw material synthesizes LiFePO for source of iron4The specific discharge capacity of/C is 152.2mAh/g, 133.8mAh/g and 122.5mAh/g respectively.
The country generally uses ferric phosphate synthesizing iron lithium phosphate at present, and must be added to excessive carbon source with ferric phosphate reaction, using phosphoric acid
One of the reason for iron is because ferric phosphate can accomplish nanoscale, so that the specific capacity increase of product.Cong Changjie etc. utilizes liquid
The phase precipitation method synthesize nano ferric phosphate, and as source of iron, pass through the nanometer spherical phosphoric acid of carbothermic method preparation uniform particle sizes
Iron lithium anode material.Material first discharge specific capacity reaches 161.8mAh/g, coulombic efficiency 98.3%.Liu etc. will
CH3COOLi·2H2O、 Fe2O3、Fe、NH4H2PO4With 3：1：1：3 ratio and the mixing of appropriate citric acid, lead under hydrogen atmosphere
Cross the LiFePO that traditional solid-phase synthesis has synthesized 50-70nm4/ C, first charge-discharge capacity have reached 162.4mAh/g.
Huang etc. mixes carbon gel with lithium acetate, ferrous acetate, ammonium dihydrogen phosphate, is mixed through molecular level, at two steps heat
Reason, finally obtains LiFePO4/ C composite, specific discharge capacity 163mAh/g under 0.1C multiplying powers, and capacity after circulating 800 times
Decay only 8%.Jiang Zhengfu etc. is using sol method synthesis nano LiMn0.9Fe0.1PO4, its charge specific capacity 174mAh/g,
Specific discharge capacity 160mAh/g, average grain diameter 95nm.Research gorgeous Chen Hong shows：Raw material particle size is smaller, and charging and discharging capacity is got over
Height, efficiency for charge-discharge are also higher.But her research is limited to micron order raw material.
Above example shows：Positive electrode raw material nano, homogenization can effectively improve the charge and discharge capacitance of positive electrode
Amount and stability.This is because raw material particle size is smaller, electrical property is better.Nano-scale particle has special property, specific surface area
Higher, interparticle contact is more preferable, mixes to each other evenly.
The content of the invention
The purpose of the utility model is to overcome shortcoming existing in the prior art, there is provided a kind of lithium iron phosphate positive material
Preparation facilities, the device is using nanometer homogenizing raw material and realizes continuous high-temperature solid phase reaction, and the utility model additionally provides
A kind of device for realizing above-mentioned preparation process, the technical solution of use are：A kind of lithium iron phosphate positive material preparation facilities, it is described
Device includes material homogenizer part, pyroreaction cooling segment and product homogenizing part, it is characterised in that：The material homogenizer portion
Dividing includes nanometer homogenizing tower, and the nanometer homogenizing tower is connected with raw material measuring tank, and the nanometer homogenizing tower is also connected with cyclone,
The output terminal connection intermediate storage tank of the nanometer homogenizing tower, the outlet connection plate and frame filter press of the intermediate storage tank, the sheet frame
Filter press connects the hopper of feeding spiro rod, and the feeding spiro rod is also connected with desolventizing machine, and the desolventizing machine connects mixed material
Storehouse；The pyroreaction cooling segment includes screw reactor, and the screw reactor connects cooling tower, and the mixing is former
The preheated device of feed bin is connected with screw reactor；The product homogenizing part includes product homogenizing tower, and the product is homogenized tower
Separator is connected, the overflow port of the separator connects product pans, and the heavy burder discharge port connection product of the separator is equal
Change tower, the cooling tower connection product homogenizing tower.
The technical characteristics of the utility model also has：The screw reactor for the series connection of more than two screw reactors and
Into multi-stage screw formula reactor.
The technical characteristics of the utility model also has：The desolventizing machine is also connected with condenser, and the condenser connects solvent
Receiving tank, the solvent receiving tank connect solvent recovery tank, and the solvent recovery tank also pipeline connects the plate and frame filter press, institute
State solvent receiving tank and be also connected with trapping heat exchanger.
The technical characteristics of the utility model also has：The product homogenizing part further includes solvent measuring tank, the measuring tank
The port of export connect product homogenizing tower, be homogenized in the product on the connecting line between tower and measuring tank and set positive displacement pump.
The beneficial effects of the utility model are：1) present apparatus produces LiFePO4 using continuous high temperature solid phase method, continuously
The material conveyed in screw reactor improves heat utilization rate, and compares traditional approach, and raw material mixing uniformity is good, thing
Material reaction is uniform；2) raw material of nanosizing homogenizing improves the efficiency for charge-discharge and stability 3 of positive electrode) present apparatus uses spiral shell
Rod-type reactor replaces traditional intermittent heating equipment (such as kiln), reduces energy consumption, and reaction stability is good.
Brief description of the drawings
Attached drawing 1 is the utility model raw material nanoization homogenizing flow diagram, and attached drawing 2 is the utility model pyroreaction work
Skill and product homogenizing process flow diagram, 11 be raw material measuring tank, and 12 be nanometer homogenizing tower, and 13 be intermediate storage tank, and 14 be rotation
Device is flowed, 15 be nanometer pulverization pump, and 16 be product pump, and 17 be plate and frame filter press, and 18 be hopper, and 19 be feeding spiro rod, and 110 be de-
Solvent machine, 111 be cooling screw, and 112 be mixed material storehouse, and 113 be condenser, and 114 be solvent receiving tank, and 115 be that solvent returns
Closed cans, 116 be trapping heat exchanger, and 117 be solvent receiving tank, and 118 be water sealed tank, and 119 be vacuum tank, and 120 be liquid seal can, 121
It is solvent pump；21 be head tank, and 22 be multi-stage screw formula reactor, and 23 be cooling tower；31 be solvent measuring tank, and 33 be cooling
Screw rod, 34 be feed screw, and 35 be product homogenizing tower, and 36 be separator, and 37 be circulating pump, and 38 be gas separator, and 39 be more
Level separator, 310 be cooling screw, and 311 be demister, and 312 be product pans, and 313 be positive displacement pump.
Embodiment
Below in conjunction with the accompanying drawings, specific embodiment of the present utility model is illustrated.
The utility model provides a kind of lithium iron phosphate positive material preparation process, which includes：By ferric phosphate
The step of lithium raw material nanoization is homogenized；The step of material that nanosizing raw material pyroreaction is generated is through cooling down tower cooler；Cooling
The step of material particles afterwards are homogenized；Wherein, nanosizing homogenizing refers to the particle that raw material is ground into 0.1-100nm sizes, receives
Riceization raw material pyroreaction is continuous reaction.Continuous reaction carries out in screw reactor, screw reactor it is anti-
It is 600-750 DEG C to answer temperature.
In the utility model, raw material source of iron is FeC2O4·2H2O,FeC2O4Or (CH3COO)2Fe, raw material phosphorus source are
NH4H2PO4Or (NH4)2HPO4, raw material lithium source is Li2CO3, LiOH or Li3PO4, LiFePO4 raw material nanoization homogenizing refer to by
Raw material is uniformly mixed, and all mixed raw materials are processed into the particle of particle diameter 0.1-100nm.
The utility model additionally provides a kind of device for realizing above-mentioned lithium iron phosphate positive material preparation process, the device bag
Material homogenizer part, pyroreaction cooling segment and product homogenizing part, pyroreaction cooling segment is included to react including screw
Device, screw reactor connection cooling tower.What the screw reactor at this place was in series for more than two screw reactors
Multi-stage screw formula reactor 22.
Material homogenizer part includes nanometer homogenizing tower 12, and nanometer homogenizing tower 12 is connected with raw material measuring tank 11, nanometer homogenizing
Tower 12 further includes the cyclone 14 being attached thereto, and the overflow pipe connection intermediate storage tank 13 of cyclone 14, it is equal that sand sediment pipe connects nanometer
Change the capable homogenizing processing again of tower 12.The output terminal connection intermediate storage tank 13 of nanometer homogenizing tower 12, the outlet connecting plate of intermediate storage tank 13
Frame filter press 17, plate and frame filter press 17 connect the hopper 18 of feeding spiro rod 19, and feeding spiro rod 19 is also connected with desolventizing machine 110, take off
Solvent machine 110 connects mixed material storehouse.Desolventizing machine 110 is also connected with condenser 113, and condenser 113 connects solvent receiving tank
114, solvent receiving tank 114 connects solvent recovery tank 115, and solvent recovery tank 115 goes back pipe connecting frame filter press 17, and solvent connects
Closed cans 114 is also connected with trapping heat exchanger 116.
Product homogenizing part includes product homogenizing tower 35, and product homogenizing tower 35 connects separator 36, the overflow of separator 36
Mouth connection product pans 312, the heavy burder discharge port connection product homogenizing tower 35 of separator 36.Product homogenizing part further includes molten
Agent measuring tank 31, the port of export connection product homogenizing tower 35 of measuring tank 31, the company between tower 35 and measuring tank 31 is homogenized in product
Adapter Lu Shangshe positive displacement pumps 313.
Raw material nano homogenizing process flow is：By required raw material input raw material measuring tank 11, while nanometer is homogenized
Solvent is full of in tower 12, raw material is put into nanometer homogenizing tower 12 afterwards, material flows into intermediate storage tank 13 after nanosizing is homogenized,
Plate and frame filter press 17 is pumped to afterwards, and material is after press filtration, and filter cake is through screw rod transmission to desolventizing machine 110, and homogenizing raw material is from de-
Solvent machine 110 is spare to mixed material storehouse 112 through screw rod transmission after coming out.Filtrate is recycled into solution recovery system.Raw material passes through
Become the particle of 0-100nm particle diameters after the processing of nanosizing homogenizing process.Concrete technology flow process is shown in attached drawing 1.
Pyroreaction technological process is：Multi-stage screw formula is delivered to after the preheated device preheating of raw material that upper step is prepared
Reactor 22, mixes up the transmission speed of screw rod, ensures that material is completely reacted during screw reactor is passed in and out.After reaction
Material is cooled down into cooling tower 23, product homogenizing tower 35 is delivered to after being cooled to room temperature, into product homogenizing process.Pyroreaction
The exhaust gas that process produces is delivered to recovery system recycling after the separation of gas separator 38.
Product homogenizing process flow is：The product of cooling tower 23 is delivered to the product homogenizing tower 35 full of solvent, product
Product pans 312 are flowed into after product homogenizing tower 35 is homogenized, are pumped to plate and frame filter press afterwards, material is after press filtration, filter cake
Through screw rod transmission to desolventizer, obtain finally being homogenized product after removing solvent, be delivered to automatic packaging line packaging therewith.Filtrate
Recycled into solvent recovering system.The utility model product homogenizing flow causes the yield rate of product to increase substantially, hardly
Produce waste material.
The multi-stage screw formula reaction utensil used in the present apparatus has the advantage that：
1) reactor is using sensing electrical heating, and the thermal efficiency is up to more than 90%.
2) with screw rod wall direct heat transfer in screw channel of the material in screw rod, heat transfer coefficient is up to 50 kilocalories/m3.h. DEG C；
3) material continuous dynamic Hybrid Heating in screw rod, has good immixture, makes material reaction uniform；
4) material can complete carbon coating or doping at the same time during reaction；
5) reactor excludes the gas of reaction generation with lower negative pressure；
6) reactor apparatus is small, and the filling rate of material is 30%, and the dosage of the protective gas such as nitrogen is greatly lowered；
7) due to the decline of nitrogen amount used, the ammonia produced in reaction process can prepare biphosphate with phosphoric acid recycling
Ammonium, the raw material as secondary response again.
8) screw rod has self clean-up action, can not only constantly clear up wall material, also the material constantly in cleaning screw slot,
Ensure the stability, uniformity of lithium anode material quality；
9) reactor realizes continuous production, and investment is greatly lowered, and produces 5000 tons of lithium anode materials, Multi-stage heating spiral shell per year
40-50 tons of bar gross weight, 50-100KW of total installed capacity, gross investment are less than 5,000,000 yuan.
Embodiment 1
On a kind of LiFePO4The preparation of/C.By anhydrous oxalic acid ferrous iron 1453kg, ammonium dihydrogen phosphate 1150kg, lithium carbonate
370kg, sucrose 140kg raw materials are put into measuring tank, while nanometer homogenizing tower is full of solvent, afterwards under nitrogen protection by original
Material is put into nanometer and is homogenized tower, and material flows into intermediate storage tank after nanosizing is homogenized, is pumped to plate and frame filter press, material afterwards
After press filtration, filter cake is homogenized after raw material comes out from desolventizer through screw rod transmission to raw material cabin through screw rod transmission to desolventizer
It is spare.Filtrate is recycled into solution recovery system.Pyroreaction screw rod will be delivered to after the preheated device preheating of the raw material prepared,
The transmission speed of screw rod is mixed up, when ensureing that reaction 10 is small at 700 DEG C in material pyroreaction screw rod.Material after reaction enters cold
But tower cooler, is delivered to product homogenizing tower, into product homogenizing process after being cooled to room temperature.The ammonia that high-temperature reaction process produces
After gas separator separates, ammonia is delivered to ammonia for the industrial waste gases such as gas, carbon monoxide, carbon dioxide and protective gas nitrogen
Gas recovery system recycles, and the industrial waste gas such as carbon monoxide, carbon dioxide is directly discharged into air with nitrogen after treatment.Cooling
The product that tower comes is delivered to the particle diameter homogenizing tower full of solvent, flows into intermediate storage tank after the homogenized tower homogenizing of product, pumps afterwards
To plate and frame filter press, for material after press filtration, filter cake obtains finally homogenizing production through screw rod transmission to desolventizer after removing solvent
Product, are delivered to automatic packaging line packaging therewith.Filtrate is recycled into solvent recovering system.Final products 1600kg is obtained, it is average
Particle diameter is 70nm, compacted density 2.6g/ml, first discharge specific capacity 166mAh/g.
Embodiment 2
On a kind of LiFePO4The preparation of/C.By anhydrous oxalic acid ferrous iron 1453kg, anhydrous phosphoric acid lithium 386kg, glucose
220kg raw materials are put into measuring tank, while nanometer homogenizing tower is full of solvent, and raw material is put into receiving under nitrogen protection afterwards
Meter Jun Hua towers, material flow into intermediate storage tank after nanosizing is homogenized, and are pumped to plate and frame filter press afterwards, material after press filtration,
Filter cake is spare to raw material cabin through screw rod transmission after being come out from desolventizer through screw rod transmission to desolventizer, homogenizing raw material.Filtrate
Recycled into solution recovery system.Pyroreaction screw rod will be delivered to after the preheated device preheating of the raw material prepared, mixes up screw rod
Transmission speed, when ensureing that reaction 15 is small at 650 DEG C in material pyroreaction screw rod.It is cold that material after reaction enters cooling tower
But, product homogenizing tower is delivered to after being cooled to room temperature, into product homogenizing process.Ammonia, an oxygen for high-temperature reaction process generation
Change the industrial waste gases such as carbon, carbon dioxide and protective gas nitrogen after gas separator separates, ammonia is delivered to Ammonia recovery
System recycles, and the industrial waste gas such as carbon monoxide, carbon dioxide is directly discharged into air with nitrogen after treatment.What cooling tower came
Product is delivered to the particle diameter homogenizing tower full of solvent, flows into intermediate storage tank after the homogenized tower homogenizing of product, is pumped to sheet frame afterwards
Filter press, after press filtration, filter cake obtains finally being homogenized product, therewith material through screw rod transmission to desolventizer after removing solvent
It is delivered to automatic packaging line packaging.Filtrate is recycled into solvent recovering system.Final products 1590kg is obtained, average grain diameter is
50nm, compacted density 2.85g/ml, first discharge specific capacity 157mAh/g.
Embodiment 3
On a kind of LiFePO4The preparation of/C.By anhydrous acetic acid ferrous iron 1739kg, anhydrous phosphoric acid lithium 400kg, glucose
200kg raw materials are put into measuring tank, while nanometer homogenizing tower is full of solvent, and raw material is put into receiving under nitrogen protection afterwards
Meter Jun Hua towers, material flow into intermediate storage tank after nanosizing is homogenized, and are pumped to plate and frame filter press afterwards, material after press filtration,
Filter cake is spare to raw material cabin through screw rod transmission after being come out from desolventizer through screw rod transmission to desolventizer, homogenizing raw material.Filtrate
Recycled into solution recovery system.Pyroreaction screw rod will be delivered to after the preheated device preheating of the raw material prepared, mixes up screw rod
Transmission speed, when ensureing that reaction 8 is small at 760 DEG C in material pyroreaction screw rod.Material after reaction enters cooling tower cooler,
Product homogenizing tower is delivered to after being cooled to room temperature, into product homogenizing process.The ammonia of high-temperature reaction process generation, an oxidation
After gas separator separates, ammonia is delivered to Ammonia recovery system for the industrial waste gases such as carbon, carbon dioxide and protective gas nitrogen
The industrial waste gases such as system recycling, carbon monoxide, carbon dioxide are directly discharged into air with nitrogen after treatment.The production that cooling tower comes
Product are delivered to the particle diameter homogenizing tower full of solvent, flow into intermediate storage tank after the homogenized tower homogenizing of product, are pumped to sheet frame pressure afterwards
Filter, after press filtration, filter cake obtains finally being homogenized product through screw rod transmission to desolventizer material after removing solvent, defeated therewith
Send to automatic packaging line and pack.Filtrate is recycled into solvent recovering system.Final products 1620kg is obtained, average grain diameter is
85nm, compacted density 2.92g/ml, first discharge specific capacity 155mAh/g.
Claims (4)
1. a kind of lithium iron phosphate positive material preparation facilities, described device includes material homogenizer part, pyroreaction cooling segment
Part is homogenized with product, it is characterised in that：The material homogenizer part includes nanometer homogenizing tower, the nanometer homogenizing tower and raw material
Measuring tank connects, and the nanometer homogenizing tower is also connected with cyclone, the output terminal connection intermediate storage tank of the nanometer homogenizing tower, institute
State the outlet connection plate and frame filter press of intermediate storage tank, the hopper of the plate and frame filter press connection feeding spiro rod, the feeding spiro rod
It is also connected with desolventizing machine, the desolventizing machine connection mixed material storehouse；The pyroreaction cooling segment is reacted including screw
Device, the screw reactor connect cooling tower, and the preheated device in mixed material storehouse is connected with screw reactor；The production
Product homogenizing part includes product homogenizing tower, the product homogenizing tower connection separator, the overflow port connection product of the separator
Pans, the heavy burder discharge port connection product homogenizing tower of the separator, the cooling tower connection product homogenizing tower.
2. device described in accordance with the claim 1, it is characterised in that：The screw reactor reacts for more than two screws
The multi-stage screw formula reactor that device is in series.
3. device described in accordance with the claim 1, it is characterised in that：The desolventizing machine is also connected with condenser, the condenser
Solvent receiving tank is connected, the solvent receiving tank connects solvent recovery tank, and the solvent recovery tank also pipeline connects the sheet frame
Filter press, the solvent receiving tank are also connected with trapping heat exchanger.
4. device described in accordance with the claim 1, it is characterised in that：The product homogenizing part further includes solvent measuring tank, institute
The port of export for stating measuring tank connects the product homogenizing tower, is homogenized on the connecting line between tower and measuring tank and sets in the product
Positive displacement pump.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114014290A (en) * | 2021-11-30 | 2022-02-08 | 中钢天源股份有限公司 | Method and equipment for preparing stable iron phosphate at low cost |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114014290A (en) * | 2021-11-30 | 2022-02-08 | 中钢天源股份有限公司 | Method and equipment for preparing stable iron phosphate at low cost |
| CN114014290B (en) * | 2021-11-30 | 2022-11-29 | 中钢天源股份有限公司 | Method and equipment for preparing stable iron phosphate at low cost |
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