CN103030128A - Industrial production method for preparing nanometer lithium iron phosphate by adopting solvent thermal method - Google Patents
Industrial production method for preparing nanometer lithium iron phosphate by adopting solvent thermal method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002904 solvent Substances 0.000 title claims abstract description 8
- 238000009776 industrial production Methods 0.000 title abstract description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims description 23
- 229940116007 ferrous phosphate Drugs 0.000 claims description 20
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 20
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 20
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 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 description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000006245 Carbon black Super-P Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- 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 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- 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 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- -1 monometallic Chemical compound 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000011164 primary particle Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000010888 waste organic solvent Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an industrial production method for preparing nanometer lithium iron phosphate by adopting a solvent thermal method. The industrial production method comprises the following steps that phosphorus source compounds, iron source compounds, lithium source compounds, carbon sources and solvents are proportionally and sequentially added into a sealed reaction kettle and are uniformly mixed and stirred, the stirring temperature rising reaction is carried out in inert atmosphere, primary products of the lithium iron phosphate are obtained, solid and liquid separation is carried out, washing and drying are carried out, the roasting is carried out in the inert atmosphere, and the lithium iron phosphate products are obtained. Waste water and waste organic solvents generated in the production process are recovered and reutilized through reduced pressure distillation. The obtained product of the lithium iron phosphate materials has fine primary particle size and narrow particle size distribution, in addition, the distribution is uniform, the conductivity is good, the electrochemical performance of products is good, the product batch consistency is good, the operation of a recovery method is simple, the control is easy, the energy consumption is low, and the method is suitable for industrial production and application.
Description
Technical field
The present invention relates to a kind of lithium-ion-power cell ferrousphosphate lithium material production method, relate to specifically the industrial process that a kind of lithium-ion-power cell that adopts solvent-thermal method to prepare is used nanometer ferrous phosphate lithium.
Background technology
Lithium ion battery is as a kind of emerging power supply; have high-voltage, heavy body, lightweight, the plurality of advantages such as volume is little, safety and environmental protection; be widely used in the fields such as mobile phone, notebook computer, digital product; along with day by day increasing the weight of of energy dilemma, the application of lithium ion battery in new-energy automobile becomes present popular research field gradually.Present commercialization battery is positive electrode material mainly with cobalt acid lithium greatly, but because cobalt resource is deficient, there are the problems such as material price costliness and security in cobalt acid lithium, so people are developing other anode material for lithium-ion batteries of excellent property always.Peridotites shape LiFePO 4 is so that its energy density is high, capacity is high, cycle performance is superior, the thermally-stabilised and advantage such as chemical stability good, use safety, cost of material is low, get more and more people's extensive concerning, in the power cell Application Areas, especially the energy-storage battery Application Areas has potentiality.
The LiFePO 4 production method of main flow is high temperature solid-state method at present, although the method is simple to operate, be easy to produce, primary particle is large, reunion is serious and size-grade distribution is uneven and wide in range, causes the shortcomings such as the lithium ion diffusion admittance is long, the product chemical property is relatively poor, the product batches consistence is relatively poor but the product behind the sintering exists.Compare with traditional high temperature solid-state method, the product primary particle pattern of solvent-thermal method preparation is controlled, granularity is less, reach Nano grade, distribution is narrow and even, mobility of particle better, tap density is higher, and the product chemical property is good, the product batches consistence is better.
Summary of the invention
The invention provides a kind of lithium-ion-power cell that adopts solvent-thermal method to prepare industrial process of nanometer ferrous phosphate lithium, the modified phosphate ferrous lithium material primary particle particle diameter that obtains is tiny, size distribution is narrow and be evenly distributed, the products obtained therefrom electrochemical specific capacity is high, batch stability is good, waste water, spent organic solvent recycling are reclaimed and purification efficiency is good, energy consumption is low, be fit to suitability for industrialized production and application.
The present invention addresses the above problem the technical scheme that adopts:
A kind of industrial process that adopts solvent-thermal method to prepare nanometer ferrous phosphate lithium comprises the steps:
(1) add successively in the closed reactor P source compound, Fe source compound, Li source compound, carbon source, solvent by a certain percentage, mixing and stirring, described P source compound, Fe source compound, Li source compound three's mol ratio is 1: 1: 2～4, the carbon source add-on is 6%～20% of solid powder (not carbonaceous sources) quality, solvent is the mixture of pure organic solvent or organic solvent and water, and the volume fraction of water≤50% wherein, the quality of solid account for the ratio of solution total mass≤90%;
(2) closed reactor inert atmosphere protection, mixture under agitation are warmed up to 100～300 ℃, and heat treated time 〉=1h crystallization occurs generates the LiFePO 4 primary products, and water vapour reclaims by the condenser system condensation that is installed on the reactor;
(3) reaction finishes to adopt solid-liquid separating method that the LiFePO 4 primary products are separated after the cooling, with organic solvent or deionized water wash repeatedly, until remove the impurity that remains in particle surface;
(4) will remove the dry materials of impurity, obtain dry powder;
(5) adopt distillation under vacuum that water, organic solvent and salt are separated recovery waste water, the organic solvent that produces in the described step (3);
(6) with the powder that obtains in the described step (4), in inert atmosphere, at 200～850 ℃ of lower roasting 0.5h～20h of maturing temperature, make the LiFePO 4 product;
Li source compound is one or more in lithium hydroxide, monometallic, Lithium Acetate, Quilonum Retard, lithium nitrate, lithium oxalate or the Trilithium phosphate in the described step (1); Fe source compound is one or more in ferrous sulfate, iron powder, iron protoxide, Ferrox, ferrous phosphate, Iron nitrate or the iron protochloride; P source compound is one or more in phosphoric acid, Secondary ammonium phosphate, primary ammonium phosphate, ammonium phosphate, tertiary iron phosphate or the monometallic; Carbon source is one or more in glucose, sucrose, carbon nanotube, graphite, RESEARCH OF PYROCARBON, carbon nano fiber, single armed carbon nanotube, both arms carbon nanotube, multi-walled carbon nano-tubes, carbon black, acetylene black, Super-P, oxysuccinic acid, tartrate, oxalic acid, Whitfield's ointment, succsinic acid, glycine, polypyrrole, ethylenediamine tetraacetic acid (EDTA) or the pitch.
The boiling point of organic solvent in the described step (1) 〉=100 ℃, preferred organic solvent boiling point 〉=150 ℃, optimum organic solvent boiling point 〉=200 ℃.
Solid-liquid separating method is press filtration or centrifugal settling in the described step (3).
Drying means is a kind of in vacuum-drying, expansion drying, lyophilize, critical spraying drying, pressure spray dryer, the centrifugal spray drying in the described step (4).
Inert atmosphere is one or more in nitrogen, argon gas or the carbonic acid gas in described step (2) and the step (6).
The principle of the inventive method is: LiFePO 4 primary products of the present invention adopt the solvent-thermal method preparation, by condition control LiFePO 4 primary products pattern and sizes such as control stirring velocity, synthesis temperature, generated times, then wash impurity in these LiFePO 4 primary products, drying obtains powder, the waste water that produces, spent organic solvent is by the underpressure distillation recycling.Dry powder is in inert atmosphere, and control roasting time, maturing temperature synthesize the ferrousphosphate lithium material product that carbon evenly coats.
The present invention has following advantage:
1. to the mix and blend reaction in closed reactor of LiFePO 4 raw material phosphor source compound, Fe source compound, Li source compound, carbon source, solvent, obtain that the primary particle particle diameter is tiny, size distribution is narrow and be evenly distributed, conduct electricity very well, the product chemical property is good, the product batches consistence is ferrousphosphate lithium material preferably;
2. compare with traditional hydrothermal method, solvent-thermal method requires lower to equipment pressure, be conducive to the industrialized production needs;
3, seriously polluted to environment-industry for the waste water that produces in the LiFePO 4 production process, spent organic solvent, the problem of easy presence of fire, the present invention adopts underpressure distillation, waste water, spent organic solvent are carried out recycling, reclaim and purification efficiency is good, energy consumption is low, recovery method is simple to operate, be easy to control, be suitable for industrial production and application.
Description of drawings
Fig. 1 is the XRD figure of the ferrousphosphate lithium material of preparation among the embodiment 1.
Fig. 2 is the SEM figure of the ferrousphosphate lithium material of preparation among the embodiment 1.
Embodiment
To help to understand the present invention below by specific embodiment and accompanying drawing, but not limit content of the present invention.
Embodiment 1
With phosphoric acid, ferrous sulfate, lithium hydroxide, glucose, H
2O and Virahol mixing and stirring in closed reactor, phosphoric acid, ferrous sulfate, lithium hydroxide three's mol ratio is 1: 1: 3, the quality of solid accounts for 30% of solution total mass, the volume ratio of water and Virahol is 1: 5, and wherein the glucose add-on is 13% of solid powder (not carbonaceous sources) quality; The closed reactor inert atmosphere protection behind the churning time 2h, is warmed up to 200 ℃, and be 3h heat-up time, makes it that crystallization occur, and water vapour reclaims by the condenser system condensation that is installed on the reactor; After the cooling, adopt centrifugal settling, use again washed with isopropyl alcohol, so circulate repeatedly, until remove particle surface impurity; The slurry of removing impurity is adopted spraying drying, obtain the powder that second particle is the class sphere; The waste water that produces in the building-up process, spent organic solvent reclaim, purify through underpressure distillation; With the powder that centrifugal spray drying obtains, be in 99.9995% nitrogen atmosphere in purity, in 600 ℃ of roasting 2h, make the ferrousphosphate lithium material product.
Material to embodiment 1 preparation carries out the XRD test, the result as shown in Figure 1, material is pure phosphoric acid ferrous lithium structure, the inclusion-free peak.Material to embodiment 1 preparation carries out the SEM test, the result as shown in Figure 2, the material primary particle is bar-shaped, it is narrow and even to distribute.
Embodiment 1 preparation material high rate performance data see Table 1.
Table 1 LiFePO 4 high rate performance
| LTD-W | Capacity(Ah) | /1C Ratio％ |
| 1C | 1.084 | 100.00％ |
| 5C | 1.028 | 94.83％ |
| 10C | 1.039 | 95.85％ |
| 15C | 1.068 | 98.52％ |
| 20C | 1.126 | 103.87％ |
| 30Ah | 1.167 | 107.66％ |
Embodiment 2
With ammonium phosphate, iron protochloride, lithium oxalate, Whitfield's ointment, dehydrated alcohol mixing and stirring in closed reactor, ammonium phosphate, iron protochloride, lithium oxalate three's mol ratio is 1: 1: 4, wherein the Whitfield's ointment add-on is 18% of solid powder (not carbonaceous sources) quality, and the quality of solid accounts for 80% of solution total mass; The closed reactor inert atmosphere protection behind the churning time 5h, is warmed up to 100 ℃, and be 6h heat-up time, makes it that crystallization occur; After the cooling, adopt press filtration to separate, use again absolute ethanol washing, so circulate repeatedly, until remove the impurity of particle surface; The slurry of removing impurity is adopted spraying drying, obtain the powder that second particle is the class sphere; The waste water that produces in the building-up process, spent organic solvent reclaim, purify through underpressure distillation; With the powder that pressure spray dryer obtains, be in 99.9995% argon gas atmosphere in purity, in 800 ℃ of roasting 1h, make the ferrousphosphate lithium material product.
Embodiment 2 preparation material high rate performance data see Table 2.
Table 2 LiFePO 4 high rate performance
| LTD-W | Capacity(Ah) | /1C Ratio％ |
| 1C | 1.070 | 98％ |
| 5C | 1.056 | 96.30％ |
| 10C | 1.034 | 95.33％ |
| 15C | 1.058 | 97.88％ |
| 20C | 1.133 | 102.33％ |
| 30Ah | 1.167 | 105.33％ |
Embodiment 3
With primary ammonium phosphate, Ferrox, Quilonum Retard, carbon nano fiber, H
2O and propyl alcohol mixing and stirring in closed reactor, primary ammonium phosphate, Ferrox, Quilonum Retard three's mol ratio is 1: 1: 2, the quality of solid accounts for 55% of solution total mass, the volume ratio of water and propyl alcohol is 1: 1.5, and wherein the carbon nano fiber add-on is 7% of solid powder (not carbonaceous sources) quality; The closed reactor inert atmosphere protection behind the churning time 7h, is warmed up to 300 ℃, and be 1h heat-up time, makes it that crystallization occur, and water vapour reclaims by the condenser system condensation that is installed on the reactor; After the cooling, adopt press filtration to separate, with the propyl alcohol washing, so circulate repeatedly, until remove the impurity of particle surface again; After removing the slurry vacuum-drying of impurity, in carbon dioxide atmosphere, in 200 ℃ of roasting 20h, make ferrousphosphate lithium material; The waste water that produces in the building-up process, spent organic solvent are through the underpressure distillation recycling.
Embodiment 3 preparation material high rate performance data see Table 3.
Table 3 LiFePO 4 product high rate performance
| LTD-W | Capacity(Ah) | /1C Ratio％ |
| 1C | 1.080 | 99％ |
| 5C | 1.033 | 95.31％ |
| 10C | 1.040 | 96.52％ |
| 15C | 1.060 | 97.66％ |
| 20C | 1.129 | 101.32％ |
| 30Ah | 1.161 | 106.22％ |
Claims (6)
1. an industrial process that adopts solvent-thermal method to prepare nanometer ferrous phosphate lithium comprises the steps:
(1) add successively in the closed reactor P source compound, Fe source compound, Li source compound, carbon source, solvent by a certain percentage, mixing and stirring, described P source compound, Fe source compound, Li source compound three's mol ratio is 1: 1: 2～4, the carbon source add-on is 6%～20% of solid powder (not carbonaceous sources) quality, solvent is the mixture of pure organic solvent or organic solvent and water, and the volume fraction of water≤50% wherein, the quality of solid account for the ratio of solution total mass≤90%;
(2) closed reactor inert atmosphere protection, mixture under agitation are warmed up to 100～300 ℃, and heat treated time 〉=1h crystallization occurs generates the LiFePO 4 primary products, and water vapour reclaims by the condenser system condensation that is installed on the reactor;
(3) reaction finishes to adopt solid-liquid separating method that the LiFePO 4 primary products are separated after the cooling, with organic solvent or deionized water wash repeatedly, until remove the impurity that remains in particle surface;
(4) will remove the dry materials of impurity, obtain dry powder;
(5) adopt distillation under vacuum that water, organic solvent and salt are separated recovery waste water, the organic solvent that produces in the described step (3);
(6) with the powder that obtains in the described step (4), in inert atmosphere, at 200～850 ℃ of lower roasting 0.5h～20h of maturing temperature, make the LiFePO 4 product;
2. a kind of industrial process that adopts solvent-thermal method to prepare nanometer ferrous phosphate lithium according to claim 1 is characterized in that the middle Li source compound of described step (1) is one or more in lithium hydroxide, monometallic, Lithium Acetate, Quilonum Retard, lithium nitrate, lithium oxalate or the Trilithium phosphate; Fe source compound is one or more in ferrous sulfate, iron powder, iron protoxide, Ferrox, ferrous phosphate, Iron nitrate or the iron protochloride; P source compound is one or more in phosphoric acid, Secondary ammonium phosphate, primary ammonium phosphate, ammonium phosphate, tertiary iron phosphate or the monometallic; Carbon source is one or more in glucose, sucrose, carbon nanotube, graphite, RESEARCH OF PYROCARBON, carbon nano fiber, single armed carbon nanotube, both arms carbon nanotube, multi-walled carbon nano-tubes, carbon black, acetylene black, Super-P, oxysuccinic acid, tartrate, oxalic acid, Whitfield's ointment, succsinic acid, glycine, polypyrrole, ethylenediamine tetraacetic acid (EDTA) or the pitch.
3. a kind of industrial process that adopts solvent-thermal method to prepare nanometer ferrous phosphate lithium according to claim 1, it is characterized in that the boiling point of organic solvent in the described step (1) 〉=100 ℃, preferred organic solvent boiling point 〉=150 ℃, optimum organic solvent boiling point 〉=200 ℃.
4. a kind of industrial process that adopts solvent-thermal method to prepare nanometer ferrous phosphate lithium according to claim 1 is characterized in that solid-liquid separating method is press filtration or centrifugal settling in the described step (3).
5. a kind of industrial process that adopts solvent-thermal method to prepare nanometer ferrous phosphate lithium according to claim 1 is characterized in that dry a kind of in vacuum-drying, expansion drying, lyophilize, critical spraying drying, pressure spray dryer, the centrifugal spray drying in the described step (4).
6. a kind of industrial process that adopts solvent-thermal method to prepare nanometer ferrous phosphate lithium according to claim 1 is characterized in that the middle inert atmosphere of described step (2) and step (6) is one or more in nitrogen, argon gas or the carbonic acid gas.
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| CN109399599A (en) * | 2018-09-12 | 2019-03-01 | 江苏合志新能源材料技术有限公司 | Lithium manganese phosphate secondary structure and preparation method thereof |
| CN109437141A (en) * | 2018-09-12 | 2019-03-08 | 江苏合志新能源材料技术有限公司 | Lithium transition metal phosphates secondary structure and preparation method thereof |
| CN112028045A (en) * | 2020-09-07 | 2020-12-04 | 厦门厦钨新能源材料股份有限公司 | Conductive lithium iron phosphate and preparation method and application thereof |
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