CN103011119A - Preparation method of nano ferric phosphate - Google Patents
Preparation method of nano ferric phosphate Download PDFInfo
- Publication number
- CN103011119A CN103011119A CN2012105487274A CN201210548727A CN103011119A CN 103011119 A CN103011119 A CN 103011119A CN 2012105487274 A CN2012105487274 A CN 2012105487274A CN 201210548727 A CN201210548727 A CN 201210548727A CN 103011119 A CN103011119 A CN 103011119A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- preparation
- nano
- ferric
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 48
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 28
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 28
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000012530 fluid Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 7
- 239000001488 sodium phosphate Substances 0.000 claims description 7
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 7
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- -1 phosphate anion Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 3
- 238000005728 strengthening Methods 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229940093916 potassium phosphate Drugs 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 239000002243 precursor Substances 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 31
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 238000012805 post-processing Methods 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019580 granularity Nutrition 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WFGBXPXOFAFPTO-UHFFFAOYSA-N [P].[Fe].[Li] Chemical compound [P].[Fe].[Li] WFGBXPXOFAFPTO-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 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
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Compounds Of Iron (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of nano ferric phosphate, and belongs to the field of preparation of anode material of lithium ion batteries. The preparation method is characterized in that a first raw material solution containing ferric ions and a second raw material solution containing phosphate ions are fed into an impinging jet reactor at a certain feed rate; the two fluids are enabled to impinge against each other at the outlet of the reactor to be fully mixed and react at a high speed; generated nano ferric phosphate and a mixed solution are collected; and filtration, washing and drying are carried out to obtain nanoscale ferric phosphate powder (FePO4.2H2O). The preparation method provided by the invention is low in cost, simple and convenient to operate and high in efficiency; and the prepared ferric phosphate is nano particles, has uniform particle diameters and a narrow distribution range and is applicable to industrial production. The nano ferric phosphate is an excellent precursor material for preparing anode material of high-power dynamic type lithium ion batteries.
Description
Technical field
The present invention relates to a kind of new preparation process of nano ferric phosphate, specifically relate to a kind of method of using the collision jet reactor to prepare nano ferric phosphate.This nano ferric phosphate is the good precursor material of preparation superpower power type lithium-ion battery anode material ferric lithium phosphate.
Background technology
Tertiary iron phosphate is a kind of traditional Chemicals, is widely used in the fields such as iron and steel, wastewater treatment, pigment, pottery, foodstuff additive.Be used in recent years prepare lithium ion battery anode material lithium iron phosphate.
Iron lithium phosphate (LiFePO
4) be a kind of novel anode material that grew up in nearly ten years, have with low cost, security good, have extended cycle life, advantages of environment protection, is power type of new generation or the first-selected positive electrode material of accumulation energy type lithium ion battery of generally acknowledging in the industry.Positive electrode material is most important in lithium ion battery, and its performance, cost and security are determining performance, cost and the security of lithium ion battery to a certain extent.
Have advantage at above-mentioned all many-sided iron lithium phosphates, but its inherent low electronics and ionic conductivity can limit iron lithium phosphate high rate charge-discharge performance.Scientists points out that by large quantity research lithium iron phosphate particles is carried out the carbon burden can improve its surface electronic specific conductivity, and the material particle size nanometer can shorten the transmission range of electronics and ion.Nowadays scientists adopts the carbon burden nano-grade lithium iron phosphate that various different ways prepare discharging and recharging under large electric current or super-large current; so that ferric phosphate lithium cell becomes the first-selected battery of present electromobile (EV) and plug-in type electromagnetic electrical automobile (PHEV) electrical source of power, also allow the low-cost preparation of mass-producing high quality nano iron lithium phosphate become the key issue that commercialization EV and PHEV need to be resolved hurrily.
As the study hotspot of at present domestic and international lithium electricity industry, research article and the patent relevant with nano lithium iron phosphate material are a lot, but really the enterprise of scale production does not almost have.The preparation technology who takes in the scale production mostly is the standby micron order iron lithium phosphate of traditional high temperature solid-phase sintering legal system ([J] A.K.Padhi et al. for example, Journal of the Electrochemical Society, Vol 144,1188-1194 (1997), [J] A.Yamada et al Journal of the Electrochemical Society, Vol 148, A960-A967 (2001), US Pat.5910382, CN1401559A), this method is selected different lithium salts, molysite, P contained compound and an amount of organic carbon source solid-phase ball milling mix sintering under certain temperature and inert atmosphere.This technique shortcoming is that the solid-phase ball milling mixing is difficult to guarantee the lithium source, the homogeneity that source of iron and phosphoric acid root are mixed, inert atmosphere is difficult for keeping in the long-time high-temperature sintering process, cause all having difficulty at aspects such as control the finished product lithium iron phosphorus ratio, purity, crystallization shape and granularities, and the different batches product is prone to a batch unstable.This is the common problem that runs in the present LiFePO 4 material industrialization process.Therefore, patent of the present invention is started with from the synthesizing iron lithium phosphate precursor and is selected suitable operational path, and specific aim solves some associated problem.
Tertiary iron phosphate is one of precursor of synthesizing iron lithium phosphate, it is close with the iron lithium phosphate structure, as long as well control structure, pattern and the granular size of tertiary iron phosphate, just can well control performance [[J] Y.H.Huang et.al. of iron lithium phosphate, Journal of Power Sources, Vol195,610 – 613 (2010)], therefore tertiary iron phosphate has more advantage than other precursors such as precursors such as Ferrox, ferrous sulfate, ferric oxide.Because the power-type power cell needs good heavy-current discharge performance, therefore, low-cost high-efficiency prepares the key point that the nano level tertiary iron phosphate just becomes extensive preparation nano-grade lithium iron phosphate.The nano ferric phosphate preparation method mainly contains liquid-phase precipitation method, hydrogen peroxide oxidation process and flame atomizing pyrolysis method.Hydrogen peroxide oxidation process [[J] S.Scaccia wherein, et al., Thermochimica Acta Vol 383,145-152 (2002)] and flame atomizing pyrolysis method [[J] F.Rohner et al.The Journal of Nutrition Vol 137 (3) 614-619 (2007)] adopt respectively divalent iron salt and organic trivalent iron salt, have the problem of high expensive.Continuously stirring formula liquid-phase precipitation method is widely used in preparing tertiary iron phosphate, but the iron phosphate grains that obtains is larger, and at several microns to tens microns, and size-grade distribution is wide, is difficult to be prepared into nano ferric phosphate [CN1305147C, CN100537419C, CN1305148C].Up-to-date being reported in adopts liquid-phase precipitation method or hydrogen peroxide oxidation process to prepare the amorphous phosphoric acid iron of nanometer [CN101837966B] in the rotating packed-bed reactor, but this arts demand is strictly controlled the pH value, device structure is complicated, thereby cause operating relative complex, the shortcomings such as maintenance cost height have increased the preparation cost of nano ferric phosphate.Yang Hui etc. also propose to adopt micro passage reaction to prepare nano ferric phosphate, and further prepare nano-grade lithium iron phosphate [CN102456873A] take this nano ferric phosphate as presoma, there is the susceptible to plugging problem of reaction channel when but micro passage reaction prepares nano-particle, and is not suitable for industrialization and produces continuously.
Two fluid streams that the make collision jet bump that flows in opposite directions at a high speed reaches high speed of relative movement in bump moment, greatly transmits between strengthening phase.Initial concept is to flow in opposite directions and be mutual bump on the impact surface in the centre of two acceleration tubes by two strands of gas-solid phase high speed coaxial high speeds, forms a highly turbulence, impingement region that granule density is the highest, for strengthen heat, the matter transmission provides fabulous condition.In the process industrial that comprises chemistry and petrochemical industry, a lot of processes are carried out under liquid phase or the phase condition take liquid as external phase; These process great majority also relate to chemical reaction.Because liquid belongs to the condensed state system, molecular motion is subject to great restriction.For the process of carrying out at molecular scale, the microcosmic troubled water becomes extremely important.To find excellent specific property that its efficient hardening microcosmic mixes as opportunity, since the nineties in 20th century, the research in percussion flow field obviously turns to the liquid continuous phase collision jet attaches most importance to.In recent years, the collision jet reactor all has application at aspects such as chemical reaction, crystallization and preparation superfine powders, but the patent and the article that utilize the collision jet reactor to prepare nano ferric phosphate there is not yet report.
Summary of the invention
The purpose of this invention is to provide a kind of technique simple, be easy to amplify, with low cost, nano ferric phosphate preparation method that production efficiency is high.
Technical scheme of the present invention is: a kind of preparation method of nano ferric phosphate, and the method prepares nano ferric phosphate with the collision jet reactor, and its concrete steps are: make first the first material solution and the second material solution; Wherein, the first material solution is made by water-soluble trivalent ferric salt for containing ferric ion solution; The second material solution is phosphorus-containing acid ion solution, is made by phosphoric acid or soluble phosphate; Above-mentioned two kinds of material solutions are exported from the collision jet reactor with the speed of 0.1m/s-50m/s, make it to bump at the collision jet reactor outlet, realize fully mixing fast and reaction of two strands of reaction solutions, collect nano ferric phosphate particle and mixed solution that reactive crystallization generates, after filtration, the white amorphous nano-scale tertiary iron phosphate powder that obtains after processing of washing, drying process; Wherein said collision jet reactor comprises two strands of identical calibers, the fluid channel of its diameter between 100m-50mm, this passage can realize that two fluid streams flow in opposite directions along the diaxon with point of crossing, and the angle of sentencing 15 °-180 ° in the point of crossing is finished bump, material transfer between strengthening fluid realizes that the quick microcosmic of two fluid streams mixes.
Ferric ion concentration is 0.1-3.0molL in preferred described the first material solution
-1Described water-soluble trivalent ferric salt is one or more in iron nitrate, iron(ic) chloride, ferric sulfate or the ironic acetate.
The concentration of phosphate anion is 0.1-3.0molL in preferred described the second material solution
-1; Described soluble phosphate is one or more in ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, sodium phosphate, disodium-hydrogen, SODIUM PHOSPHATE, MONOBASIC, potassiumphosphate, potassium phosphate,monobasic or the potassium primary phosphate.
Preferable reaction temperature is controlled between the 0-80 ° of C.
The nano ferric phosphate FePO that above-mentioned collision jet reactor generates
4.2H
2O, white amorphous powder, granularity is between 10-50nm.
The basic meaning of collision jet method is that two fluid streams are flowed in opposite directions along the diaxon with point of crossing, and locate in the point of crossing, be mutually to clash into 15 °-180 ° angle on the so-called impact surface, formed the impingement region of height turbulence, the impingement region microcosmic mixes strongly, rapid reaction generates a large amount of nucleus.
Beneficial effect:
1. the collision jet reactor is made of two bursts of same size fluid channels with point of crossing, and the fluid channel caliber is 100 μ m-50mm, and emitted fluid impact angle is 15 °-180 °, and it is simple in structure, and the equipment investment cost is low.
2. collision jet reactor, volume is little, the low-temperature atmosphere-pressure reaction, energy consumption is little, and preparation cost is low.
The collision jet reactor process simple, without blockage problem, easy to operate, be easy to amplify, production efficiency is high, the reaction that general traditional liquid-phase precipitation reaction needed was finished in several hours to tens hours adopts this reactor several seconds just can finish to several minutes.In addition, used all raw materials of the present invention all are common Chemicals cheap and easy to get, and reaction process does not have side reaction to occur and do not produce hazardous and noxious substances, environmental friendliness.
4. the nano ferric phosphate composition for preparing is stable, purity is high, globule size is even, narrow particle size distribution.
Description of drawings
Fig. 1 is the structural representation of collision jet equipment, 100 μ m≤d≤50mm wherein, 15 °≤φ≤180 °;
Fig. 2 is the XRD figure of embodiment one prepared nano ferric phosphate;
Fig. 3 is embodiment one prepared nano ferric phosphate transmission electron microscope picture.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further, following examples do not produce restriction to the present invention.The structural representation of the collision jet equipment that the present invention is used as shown in Figure 1.
Embodiment one:
Preparation 0.3molL
-1Iron nitrate solution, the preparation 0.3molL
-1Ammonium hydrogen phosphate solution, with two solution respectively with 2ms
-1Speed be transported in the collision jet reactor (d=1mm, φ=180 °), the temperature of control reaction system is 25 ℃, precipitation reaction occurs in the reactor exit high-speed mixing in stock liquid.Collect reaction solution, after filtration, washing and dry postprocessing working procedures obtain the nano level tertiary iron phosphate.The XRD figure of the nano level tertiary iron phosphate that present embodiment is prepared and transmission electron microscope picture are respectively as shown in Figures 2 and 3.
Embodiment two:
Configuration 0.5molL
-1Ferric chloride Solution, configuration 0.5molL
-1Sodium radio-phosphate,P-32 solution, with two solution respectively with 50ms
-1Speed be transported in the collision jet reactor (d=100 μ m, φ=15 °), the temperature of control reaction system is 0 ℃, precipitation reaction occurs in the reactor exit high-speed mixing in stock liquid.Collect reaction solution, after filtration, washing and dry postprocessing working procedures obtain the nano level tertiary iron phosphate.
Embodiment three:
Configuration 3molL
-1Ferrum sulfuricum oxydatum solutum, configuration 3molL
-1Potassium dihydrogen phosphate, with two solution respectively with 0.1ms
-1Speed be transported in the collision jet reactor (d=10mm, φ=60 °), the temperature of control reaction system is 80 ℃, precipitation reaction occurs in the reactor exit high-speed mixing in stock liquid.Collect reaction solution, after filtration, washing and dry postprocessing working procedures obtain the nano level tertiary iron phosphate.
Embodiment four:
Configuration 2molL
-1Ironic acetate solution disposes phosphorous acid group mixing solutions, and it consists of 0.5molL
-1Ammonium phosphate and 0.5molL
-1SODIUM PHOSPHATE, MONOBASIC, with two solution respectively with 25ms
-1, 50ms
-1Speed be transported in the collision jet reactor (d=50mm, φ=90 °), the temperature of control reaction system is 50 ℃, precipitation reaction occurs in the reactor exit high-speed mixing in stock liquid.Collect reaction solution, after filtration, washing and dry postprocessing working procedures obtain the nano level tertiary iron phosphate.
Embodiment five:
Configuration iron content Ar ion mixing solution, it consists of 0.5molL
-1Ferric sulfate and 0.5molL
-1Iron nitrate, configuration 1molL
-1Ammonium dihydrogen phosphate, with two solution respectively with 20ms
-1Speed be transported in the collision jet reactor (d=80 μ m, φ=75 °), the temperature of control reaction system is 30 ℃, precipitation reaction occurs in the reactor exit high-speed mixing in stock liquid.Collect reaction solution, after filtration, washing and dry postprocessing working procedures obtain the nano level tertiary iron phosphate.
Embodiment six:
Configuration iron content Ar ion mixing solution, it consists of 0.5molL
-1Ferric sulfate, 0.5molL
-1Iron nitrate, 0.5molL
-1Iron(ic) chloride and 0.5molL
-1Second iron disposes phosphorous acid group mixing solutions, and it consists of 1molL
-1SODIUM PHOSPHATE, MONOBASIC and 1molL
-1Potassiumphosphate, with two solution respectively with 1ms
-1Speed be transported in the collision jet reactor (d=3mm, φ=15 °), the temperature of control reaction system is 10 ℃, precipitation reaction occurs in the reactor exit high-speed mixing in stock liquid.Collect reaction solution, after filtration, washing and dry postprocessing working procedures obtain the nano level tertiary iron phosphate.
Embodiment seven:
Configuration iron content Ar ion mixing solution, it consists of 1molL
-1Ferric sulfate, 0.7molL
-1Iron nitrate and 1molL
-1Iron(ic) chloride disposes phosphorous acid group mixing solutions, and it consists of 0.3molL
-1Ammonium phosphate, 0.3molL
-1Ammonium hydrogen phosphate, 0.3molL
-1Primary ammonium phosphate, 0.3molL
-1Sodium phosphate, 0.3molL
-1Disodium-hydrogen, 0.3molL
-1SODIUM PHOSPHATE, MONOBASIC, 0.3molL
-1Potassiumphosphate, 0.3molL
-1Potassium phosphate,monobasic and 0.3molL
-1Potassium primary phosphate, with two solution respectively with 0.5ms
-1Speed be transported in the collision jet reactor (d=5mm, φ=90 °), the temperature of control reaction system is 20 ℃, precipitation reaction occurs in the reactor exit high-speed mixing in stock liquid.Collect reaction solution, after filtration, washing and dry postprocessing working procedures obtain the nano level tertiary iron phosphate.
Embodiment eight:
Configuration iron content Ar ion mixing solution, it consists of 1.8molL
-1Ferric sulfate and 1.2molL
-1Iron nitrate disposes phosphorous acid group mixing solutions, and it consists of 0.75molL
-1Ammonium hydrogen phosphate and 0.75molL
-1Potassium phosphate,monobasic, with two solution respectively with 20ms
-1, 40ms
-1Speed be transported in the collision jet reactor (d=30 μ m, φ=150 °), the temperature of control reaction system is 40 ℃, precipitation reaction occurs in the reactor exit high-speed mixing in stock liquid.Collect reaction solution, after filtration, washing and dry postprocessing working procedures obtain the nano level tertiary iron phosphate.
Embodiment nine:
Configuration 3molL
-1Iron nitrate solution disposes phosphorous acid group mixing solutions, and it consists of 1.5molL
-1Ammonium phosphate and 1.5molL
-1SODIUM PHOSPHATE, MONOBASIC, with two solution respectively with 5ms
-1, 5ms
-1Speed be transported in the collision jet reactor (d=2mm, φ=120 °), the temperature of control reaction system is 60 ℃, precipitation reaction occurs in the reactor exit high-speed mixing in stock liquid.Collect reaction solution, after filtration, washing and dry postprocessing working procedures obtain the nano level tertiary iron phosphate.
Embodiment ten:
Configuration 0.1molL
-1Iron nitrate solution, configuration 0.1molL
-1Potassium phosphate solution, with two solution respectively with 3ms
-1Speed be transported in the collision jet reactor (d=8mm, φ=30 °), the temperature of control reaction system is 70 ℃, precipitation reaction occurs in the reactor exit high-speed mixing in stock liquid.Collect reaction solution, after filtration, washing and dry postprocessing working procedures obtain the nano level tertiary iron phosphate.
The preparation-obtained particle size were of embodiment 1-10 as shown in Table 1.
Table one
Claims (5)
1. the preparation method of a nano ferric phosphate, its concrete steps are: make first the first material solution and the second material solution; Wherein, the first material solution is made by water-soluble trivalent ferric salt for containing ferric ion solution; The second material solution is phosphorus-containing acid ion solution, is made by phosphoric acid or soluble phosphate; Above-mentioned two kinds of material solutions are exported from the collision jet reactor with the speed of 0.1m/s-50m/s, make it to bump at the collision jet reactor outlet, realize fully mixing fast and reaction of two strands of reaction solutions, collect nano ferric phosphate particle and mixed solution that reactive crystallization generates, after filtration, the white amorphous nano-scale tertiary iron phosphate powder that obtains after processing of washing, drying process; Wherein said collision jet reactor comprises two strands of identical calibers, the fluid channel of its diameter between 100m-50mm, this passage can realize that two fluid streams flow in opposite directions along the diaxon with point of crossing, and the angle of sentencing 15 °-180 ° in the point of crossing is finished bump, material transfer between strengthening fluid realizes that the quick microcosmic of two fluid streams mixes.
2. such as claim 1 described preparation method, it is characterized in that ferric ion concentration is 0.1-3.0molL in described the first material solution
-1Described water-soluble trivalent ferric salt is one or more in iron nitrate, iron(ic) chloride, ferric sulfate or the ironic acetate.
3. such as claim 1 described preparation method, it is characterized in that the concentration of phosphate anion is 0.1-3.0molL in described the second material solution
-1; Described soluble phosphate is one or more in ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, sodium phosphate, disodium-hydrogen, SODIUM PHOSPHATE, MONOBASIC, potassiumphosphate, potassium phosphate,monobasic or the potassium primary phosphate.
4. such as claim 1 described preparation method, it is characterized in that temperature of reaction is controlled between the 0-80 ° of C.
5. such as claim 1 described preparation method, it is characterized in that the nano ferric phosphate FePO that described collision jet reactor generates
4.2H
2O, white amorphous powder, granularity is between 10-50nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210548727.4A CN103011119B (en) | 2012-12-17 | 2012-12-17 | Preparation method of nano ferric phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210548727.4A CN103011119B (en) | 2012-12-17 | 2012-12-17 | Preparation method of nano ferric phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103011119A true CN103011119A (en) | 2013-04-03 |
| CN103011119B CN103011119B (en) | 2015-04-22 |
Family
ID=47960303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210548727.4A Active CN103011119B (en) | 2012-12-17 | 2012-12-17 | Preparation method of nano ferric phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103011119B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103259017A (en) * | 2013-05-13 | 2013-08-21 | 清华大学深圳研究生院 | Nano iron phosphate micro chemical preparation method and nano iron phosphate |
| CN104362317A (en) * | 2014-11-05 | 2015-02-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Iron phosphate/conducting polymer composite cathode material for lithium ion battery and preparation method of composite cathode material |
| CN107473196A (en) * | 2017-09-30 | 2017-12-15 | 贵州微化科技有限公司 | A kind of method of continuous production LITHIUM BATTERY high compacted density nano ferric phosphate |
| CN107978753A (en) * | 2017-11-30 | 2018-05-01 | 湘潭大学 | A kind of bowl-shape hollow carbon sphere/graphene composite materials of ferric phosphate@and its preparation method and application |
| CN112264005A (en) * | 2020-12-08 | 2021-01-26 | 南京工业大学 | Method for preparing zinc tungstate catalyst by using micro-channel precipitation method |
| CN112479175A (en) * | 2020-12-29 | 2021-03-12 | 铜陵纳源材料科技有限公司 | Continuous synthesis device and synthesis method of iron phosphate |
| CN114101699A (en) * | 2021-11-26 | 2022-03-01 | 昆明银科电子材料股份有限公司 | Method for preparing high-crystallization silver powder for heat-conducting adhesive through rapid reduction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201815310U (en) * | 2010-10-21 | 2011-05-04 | 王晓薇 | Slurry mixing device with homodisperse ferric phosphate mixing function |
| CN102391179A (en) * | 2011-09-06 | 2012-03-28 | 东南大学 | Method for preparing pyrithione salt dispersed solution by injection coprecipitation method |
| CN102807203A (en) * | 2012-07-06 | 2012-12-05 | 云南磷化集团有限公司 | Preparation method for nanocluster structure iron phosphate |
-
2012
- 2012-12-17 CN CN201210548727.4A patent/CN103011119B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201815310U (en) * | 2010-10-21 | 2011-05-04 | 王晓薇 | Slurry mixing device with homodisperse ferric phosphate mixing function |
| CN102391179A (en) * | 2011-09-06 | 2012-03-28 | 东南大学 | Method for preparing pyrithione salt dispersed solution by injection coprecipitation method |
| CN102807203A (en) * | 2012-07-06 | 2012-12-05 | 云南磷化集团有限公司 | Preparation method for nanocluster structure iron phosphate |
Non-Patent Citations (1)
| Title |
|---|
| 王星明等: "撞击流管式反应制备超细氧化锆粉体", 《稀有金属》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103259017A (en) * | 2013-05-13 | 2013-08-21 | 清华大学深圳研究生院 | Nano iron phosphate micro chemical preparation method and nano iron phosphate |
| CN103259017B (en) * | 2013-05-13 | 2015-10-28 | 清华大学深圳研究生院 | Micro-chemical manufacturing process of nano ferric phosphate and nano ferric phosphate |
| CN104362317A (en) * | 2014-11-05 | 2015-02-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Iron phosphate/conducting polymer composite cathode material for lithium ion battery and preparation method of composite cathode material |
| CN107473196A (en) * | 2017-09-30 | 2017-12-15 | 贵州微化科技有限公司 | A kind of method of continuous production LITHIUM BATTERY high compacted density nano ferric phosphate |
| CN107978753A (en) * | 2017-11-30 | 2018-05-01 | 湘潭大学 | A kind of bowl-shape hollow carbon sphere/graphene composite materials of ferric phosphate@and its preparation method and application |
| CN107978753B (en) * | 2017-11-30 | 2020-02-07 | 湘潭大学 | Ferric phosphate @ bowl-shaped hollow carbon sphere/graphene composite material and preparation method and application thereof |
| CN112264005A (en) * | 2020-12-08 | 2021-01-26 | 南京工业大学 | Method for preparing zinc tungstate catalyst by using micro-channel precipitation method |
| CN112479175A (en) * | 2020-12-29 | 2021-03-12 | 铜陵纳源材料科技有限公司 | Continuous synthesis device and synthesis method of iron phosphate |
| CN114101699A (en) * | 2021-11-26 | 2022-03-01 | 昆明银科电子材料股份有限公司 | Method for preparing high-crystallization silver powder for heat-conducting adhesive through rapid reduction |
| CN114101699B (en) * | 2021-11-26 | 2024-04-26 | 昆明银科电子材料股份有限公司 | Method for preparing high-crystallization silver powder for heat-conducting glue by rapid reduction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103011119B (en) | 2015-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103011119B (en) | Preparation method of nano ferric phosphate | |
| Jing et al. | E-pH diagrams for the Li-Fe-P-H2O system from 298 to 473 K: thermodynamic analysis and application to the wet chemical processes of the LiFePO4 cathode material | |
| CN101145611B (en) | Lithium ion cell anode material lithium vanadium phosphate preparation method | |
| Zhang et al. | Advances in new cathode material LiFePO4 for lithium-ion batteries | |
| CN101106194B (en) | Cathode material Li3V2(PO4)3 of lithium ion battery and its making method | |
| CN101693531A (en) | Method for preparing nano iron phosphate | |
| CN102583292B (en) | Ferric phosphate having micro-nano structure and preparation method thereof as well as lithium iron phosphate material | |
| CN101837966B (en) | Method for preparing nanometer ferric phosphate | |
| CN105895886A (en) | Transition metal phosphide/porous carbon anode composite material for sodium-ion battery and preparation method thereof | |
| CN102683674A (en) | Preparation methods of nano iron phosphate precursors and ultra-fine nano lithium iron phosphate usable for electrode material | |
| CN104934574A (en) | Preparation method of ultra-high density cobaltosic oxide/porous graphene nano-composite anode material for lithium ion battery | |
| CN102311109B (en) | Method for preparing LiFePO4/C composite cathode material by continuous reaction | |
| CN101695998A (en) | Method for preparing nano ferric phosphate | |
| CN102244246B (en) | Preparation method of lithium iron phosphate/carbon composite material | |
| CN106564867A (en) | Method for preparing iron phosphate material by adding reducing organic matters | |
| CN104538629A (en) | Method for preparing spherical nano iron phosphate | |
| CN104332629A (en) | Preparation method of hollow lithium manganese phosphate nano balls and product | |
| CN103219514A (en) | Method for assisted preparation of carbon composite lithium iron phosphate micro-nanometer powder through industrially modified starch | |
| CN101332986A (en) | Method for preparing positive electrode material of LiFePO4 by phosphating reaction | |
| CN105336944A (en) | High-capacity cathode material for lithium ion batteries and preparation method thereof | |
| CN109052358B (en) | Preparation method of mesoporous-macroporous iron phosphate | |
| CN103050697B (en) | Method for preparing micron-sized LiFePO4/C serving as high-rate lithium ion battery anode material | |
| Wang et al. | A review for the synthesis methods of lithium vanadium phosphate cathode materials | |
| CN113991117A (en) | Preparation method of lithium iron phosphate composite material | |
| CN101734927B (en) | Method for preparing lithium iron phosphate/carbon nano tube compound material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |