CN1762798A - The preparation method of lithium iron phosphate - Google Patents
The preparation method of lithium iron phosphate Download PDFInfo
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- CN1762798A CN1762798A CNA2005100297254A CN200510029725A CN1762798A CN 1762798 A CN1762798 A CN 1762798A CN A2005100297254 A CNA2005100297254 A CN A2005100297254A CN 200510029725 A CN200510029725 A CN 200510029725A CN 1762798 A CN1762798 A CN 1762798A
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- lithium phosphate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims description 19
- 238000000034 method Methods 0.000 claims abstract description 34
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 18
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 235000011837 pasties Nutrition 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 238000003746 solid phase reaction Methods 0.000 abstract description 4
- 230000001788 irregular Effects 0.000 abstract description 3
- 239000010450 olivine Substances 0.000 abstract description 2
- 229910052609 olivine Inorganic materials 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 13
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 10
- 229910010710 LiFePO Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000010671 solid-state reaction Methods 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013292 LiNiO Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- -1 pattern is irregular Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses the preparation process of ferric lithium phosphate. The preparation process includes the following steps: A. preparing the precursor of ferric lithium phosphate and B. transferring the precursor of ferric lithium phosphate into tube furnace and roasting at 500-800 deg.c under the protection of nitrogen for 5-24 hr to obtain the product. Unlike conventional high temperature solid phase reaction process, which obtains ferric lithium phosphate product with impurity, irregular form, large and uneven grains and poor conducting property and reversibility, the preparation process of the present invention can prepare ferric lithium phosphate with high purity, excellent crystal structure, high crystallization degree of olivine crystal form, great specific surface area and excellent electrochemical performance. XRD test shows that the ferric lithium phosphate of the present invention has average crystal lattice size of 43.9 nm, maximum probability crystal lattice size of 40.7 nm and narrow size distribution.
Description
Technical field
The present invention relates to a kind of method for production of phosphate salt that contains metal more than two kinds, relate to a kind of method preparing phosphate iron lithium that is used for battery material in particular.
Background technology
Continually developing of new forms of energy is the important foundation of human kind sustainable development.Along with the progress of science and technology, people are more and more strong to the demand of the removable energy.Lithium ion battery is since coming out the beginning of the nineties in last century, because of it has the choosing that high energy density, excellent cycle performance and retention of charge are considered to the ideal of heavy body high power battery.The positive electrode material of present business-like lithium ion battery is with LiCoO
2Be main, this material has reliably performance and long cycle life, but also has two shortcomings that are difficult for overcoming, and the one, cobalt resource lacks relatively, makes the raw materials cost height, and the 2nd, cobalt has certain toxicity, exists dangerous when battery is abused.Therefore, the researchist is striving to find always and is substituting LiCoO
2Material.LiNiO wherein
2And LiMn
2O
4Two kinds of materials once were the emphasis of exploitation, but from present research, the solution that the deficiency of these two kinds of materials on synthesis technique and performance do not find always can't invested in plant production.
LiFePO
4Be the LiNiO that continues
2And LiMn
2O
4Another research focus that the back produces.Reported first such as Goodenough in 1997 have a LiFePO of olivine structural
4Li can reversibly embed and move out
+, J.Electrochem.Soc., 144,1188 (1997).From resource, environment and performance, LiFePO
4To become lithium ion battery ideal positive electrode material.People such as Thackeray think LiFePO
4Discovery, indicate the lithium ion battery arrival of a New Times, Nature Materials, 1,81 (2002).The present LiFePO that studies show that
4Have discharge platform very stably, the more important thing is LiFePO
4Because its constitutional features makes it have better security, and material non-toxic, has friendly environment for use.Yet LiFePO
4Lower electron conduction becomes a bottleneck of its commercialized development.Therefore Recent study personnel's work mainly concentrates in the innovation by synthetic methods such as doping, carbon coatings and improves LiFePO
4Electronic conductivity.
LiFePO
4Synthetic method mainly contain solid-phase synthesis, hydrothermal method, carbon reduction method and sol-gel method etc., wherein solid-phase synthesis is the most sophisticated method, this method is simple and convenient, easily operation.But owing to be solid state reaction, this method synthesis cycle is long, and batch stability of product is difficult to control, and the kind of raw material must be a decomposability salt and the scope of application is narrow and small owing to being limited in also; Liquid phase method is an efficient and simple method, in inorganic materials synthetic, utilize liquid phase method to obtain many well behaved materials, because liquid phase method is synthetic to be uniform mixing reactant on molecular level, have the batch stable of product, control easily, advantages such as synthetic route is easy to adjust, and the reactant selectable range is wide.Sol-gel method in the liquid phase method and hydrothermal method can obtain the LiFePO of complete in crystal formation
4, but be subjected to complicated process of preparation or the high restriction of equipment requirements; Co-precipitation rule in the liquid phase method is not subjected to above-mentioned restriction, is referred to as " softening learning " synthesis method.It is simple, easy to operate that coprecipitation method also has equipment, and reaction is easy to control, and be convenient to mix, modification such as carbon coating, modify series of advantages such as processings, be to synthesize LiFePO
4A kind of desirable method.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of utilizing the coprecipitation method principle to prepare nano-scale lithium iron phosphate.
The technical solution used in the present invention: a kind of method preparing phosphate iron lithium comprises the following steps:
(a) preparation ferric lithium phosphate precursor: the phosphoric acid solution with 0.05～3mol/L under normal pressure and temperature adds reduced iron powder and doping element compound or conductive agent under nitrogen atmosphere, under agitation mixed, controlled temperature is 30～100 ℃, reacted 1～5 hour, the LiOH solution reaction 4～6 hours that dropwise adds 0.05～5mol/L then, in solution, drip phosphoric acid solution after above-mentioned reaction finishes and adjust the pH value of solution value to neutral, when treating that solution obviously changes thick suspension into temperature being risen to 100 ℃ steams suspension to pasty state, then product is extracted out, after the process dehydrated alcohol repeatedly washs, use the vacuum pump suction filtration, product obtains described ferric lithium phosphate precursor presoma after putting into the vacuum drying oven drying;
(b) ferric lithium phosphate precursor being transferred in the tube furnace, is 500～800 ℃, roasting 5～24 hours in inertia or non-oxidizing atmosphere, with the heating of the temperature rise rate of 1～30 ℃/min, controlled temperature, obtains final product.
Beneficial effect of the present invention: the iron lithium phosphate product that conventional high temperature solid state reaction obtains often contains impurity, pattern is irregular, particle is big, granularity is inhomogeneous, electroconductibility and reversibility are poor.And the iron lithium phosphate of the present invention preparation has the olivine-type crystal formation of fine crystalline phase body structure and good size distribution, and this homogeneous phase, degree of crystallinity height, epigranular, the LiFePO 4 material that particle diameter is little, specific surface is high have good chemical property.LiFePO according to the acquisition of XRD test data
4Size distribution, the average lattice dimensions of iron lithium phosphate of the present invention preparation is 43.9nm, the lattice dimensions at maximum frequency place is 40.7nm, size distribution is narrower.This shows that also the present invention adopts the co-precipitation low-temperature sintering technology can synthesize high performance iron lithium phosphate product, and the pattern of iron lithium phosphate product and microtexture are easier to control.
Description of drawings
Fig. 1 is the XRD spectra from ferrous salt raw material synthetic iron lithium phosphate;
Fig. 2 is the XRD spectra from straight iron powder raw material synthetic iron lithium phosphate;
Fig. 3 is an iron lithium phosphate crystal grain scatter chart.
Embodiment
Below by accompanying drawing the present invention is described in further detail: a kind of method preparing phosphate iron lithium comprises the following steps: (a) preparation ferric lithium phosphate precursor; (b) ferric lithium phosphate precursor is transferred in the tube furnace, temperature was controlled at 500～800 ℃, roasting 5～10 hours under nitrogen protection, obtained synthetic product.Wherein step (a) iron lithium phosphate precursor synthetic has two kinds of methods: first kind under normal pressure and temperature with the ferrous salt of certain stoichiometric ratio (as FeCl
2, FeSO
4Or Fe (NO
3)
2Deng), hydrophosphate (Na
2HPO
4, (NH
4)
2HPO
4Deng), lithium salts (LiCl, LiNO
3Deng) be dissolved in the deionized water respectively and letting nitrogen in and deoxidizing, under the nitrogen atmosphere that hydrophosphate, ferrous salt solution is under agitation mixed then, react after 1-5 hour, dropwise add lithium salt solution, the continuation reaction is 4-6 hour then, extracts out also and filters, after process dehydrated alcohol and deaerated water repeatedly wash, after putting into vacuum drying oven and being dried to moisture and volatilizing fully, obtain presoma; Second kind is (a) preparation ferric lithium phosphate precursor: the phosphoric acid solution with 0.05～3mol/L under normal pressure and temperature adds reduced iron powder and doping element compound or conductive agent under nitrogen atmosphere, under agitation mixed, controlled temperature is 30～100 ℃, reacted 1～5 hour, the LiOH solution reaction 4～6 hours that dropwise adds 0.05～5mol/L then, in solution, drip phosphoric acid solution after above-mentioned reaction finishes and adjust the pH value of solution value to neutral, when treating that solution obviously changes thick suspension into temperature being risen to 100 ℃ steams suspension to pasty state, then product is extracted out, after the process dehydrated alcohol repeatedly washs, use the vacuum pump suction filtration, product obtains described ferric lithium phosphate precursor presoma after putting into the vacuum drying oven drying.
The XRD analysis of product is carried out on the German Bruker product ADVANCE of company X-ray diffractometer, the Cu target, and the Ka line, sweep limit is 10～69.997 °, is 0.014 °/s 25 ℃ of following sweep velocitys.The qualitative analysis of thing phase is by getting with the card contrast the diffraction peak PDF on the X diffractometer.The grain-size of material obtains the XRD data analysis by software for calculation.
It is generally acknowledged that the material with characteristics such as homogeneous phase, degree of crystallinity height, epigranular, particle diameter are little, specific surface height just has good chemical property.Therefore, we can synthesize the olivine-type LiFePO with fine crystalline phase body structure and good size distribution at the primary study exploitation
4The technology of material.The product that conventional high temperature solid state reaction obtains often contains impurity, pattern is irregular, particle is big, granularity is inhomogeneous, electroconductibility and reversibility are poor.By contrast, adopt the co-precipitation low-temperature sintering technology can synthesize premium quality product, especially the composition of product, pattern and microtexture are easier to control.
First method synthetic material is through XRD analysis, and the gained XRD spectra as shown in Figure 1.XRD spectra shows that wherein main component is not all to be LiFePO
4But contain more Fe
3(PO
4)
2, reason is to have adopted FeCl in building-up process
2(NH
4)
2HPO
4During as raw material, the Li ion can be easy to generate [Li (NH with ammonia under the environment that has ammonia to exist in solution
3)
4]
+The complex ion of type, it and Cl
-Ionic bond is soluble in various organic solvents, after with washing with alcohol, has caused a large amount of losses of lithium ion.And the test discovery, Trilithium phosphate is when having ammonium salt to exist, and solubleness can increase, and generates double salt together with ammonium phosphate, and the solubleness of these double salt in water is general all big than the solubleness of Trilithium phosphate in water.In addition, solution system is alkalescence, easily forms the oxyhydroxide of iron; These factors can influence the composition of synthetic product.After adopting other ferrous salt and hydrophosphate, institute's synthetic iron lithium phosphate precursor purity is higher.But because the generation of its esters brings difficulty to washing impurity-removing.
The present invention has adopted second method, and the synthesizing iron lithium phosphate presoma can effectively be avoided the introducing of impurity, has adopted straight iron powder.The XRD test result is as shown in Figure 2: the composition of synthetic all is LiFePO in the spectrogram
4In building-up process, every reacting completely, and under no ammonia environment, lithium ion does not run off; by the adjusting of pH, the solution slant acidity can not produce oxyhydroxide; nitrogen protection is complete, and ferrous ion is not oxidized, and this method can obtain ideal iron lithium phosphate precursor.In presoma synthetic, the pH value of solution will have influence on the composition of synthetic product to a certain extent.K according to each material
SpValue (table 1) in building-up process, requires to avoid forming the precipitation of hydroxide of metal ion on the one hand, and the pH value is less than 6; Require phosphate radical ionization as much as possible on the other hand, make it and metal ion between precipitin reaction fully carry out, the pH value is greater than 6.According to Fe-H
2The Bo Baitu of O system, the pH value of control solution system avoids generating ferrous hydroxide less than 6, just can control the oxyhydroxide that occurs iron in the precursor.
The k of table 1 allied compound
SpValue
| Compound | Li 3PO 4 | Fe(OH) 2 | Fe(OH) 3 | FePO 4 |
| k spValue | 3.2×10 -9 | 8×10 -16 | 4×10 -38 | 1.3×10 -22 |
Fig. 3 is the LiFePO that obtains according to the XRD test data
4Size distribution.Average lattice dimensions with coprecipitation method synthetic sample is 43.9nm, and the lattice dimensions at maximum frequency place is 40.7nm, and size distribution is narrower.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (1)
1. a method preparing phosphate iron lithium comprises the following steps:
(a) preparation ferric lithium phosphate precursor: the phosphoric acid solution with 0.05～3mol/L under normal pressure and temperature adds reduced iron powder and doping element compound or conductive agent under nitrogen atmosphere, under agitation mixed, controlled temperature is 30～100 ℃, reacted 1～5 hour, the LiOH solution reaction 4～6 hours that dropwise adds 0.05～5mol/L then, in solution, drip phosphoric acid solution after above-mentioned reaction finishes and adjust the pH value of solution value to neutral, when treating that solution obviously changes thick suspension into temperature being risen to 100 ℃ steams suspension to pasty state, then product is extracted out, after the process dehydrated alcohol repeatedly washs, use the vacuum pump suction filtration, product obtains described ferric lithium phosphate precursor presoma after putting into the vacuum drying oven drying;
(b) ferric lithium phosphate precursor being transferred in the tube furnace, is 500～800 ℃, roasting 5～24 hours in inertia or non-oxidizing atmosphere, with the heating of the temperature rise rate of 1～30 ℃/min, controlled temperature, obtains final product.
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|---|---|---|---|
| CNB2005100297254A CN100570930C (en) | 2005-09-16 | 2005-09-16 | Preparation method of lithium iron phosphate |
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|---|---|---|---|
| CNB2005100297254A CN100570930C (en) | 2005-09-16 | 2005-09-16 | Preparation method of lithium iron phosphate |
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| Publication Number | Publication Date |
|---|---|
| CN1762798A true CN1762798A (en) | 2006-04-26 |
| CN100570930C CN100570930C (en) | 2009-12-16 |
Family
ID=36747164
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|---|---|
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7722848B2 (en) | 2007-09-25 | 2010-05-25 | Byd Company Limited | Lithium iron phosphate cathode material |
| US8052897B2 (en) | 2008-02-29 | 2011-11-08 | Byd Company Limited | Composite compound with mixed crystalline structure |
| US8057711B2 (en) | 2008-02-29 | 2011-11-15 | Byd Company Limited | Composite compound with mixed crystalline structure |
| US8062560B2 (en) | 2008-02-29 | 2011-11-22 | Byd Company Limited | Composite compound with mixed crystalline structure |
| US8062559B2 (en) | 2008-02-29 | 2011-11-22 | Byd Company Limited | Composite compound with mixed crystalline structure |
| US8088305B2 (en) | 2008-02-22 | 2012-01-03 | Byd Company Limited | Lithium iron phosphate cathode material |
| US8148015B2 (en) | 2008-03-21 | 2012-04-03 | Byd Company Limited | Cathode materials for lithium batteries |
| US8153032B2 (en) | 2008-06-06 | 2012-04-10 | Byd Company Limited | Transition metal hydroxide and oxide, method of producing the same, and cathode material containting the same |
| CN102447099A (en) * | 2010-10-09 | 2012-05-09 | 河南环宇集团有限公司 | Novel method for preparing lithium ferrous phosphate complex salt positive electrode material by using scrap iron, phosphoric acid and lithium hydroxide |
| US8216725B2 (en) | 2008-01-25 | 2012-07-10 | Byd Company Limited | Electrolyte for batteries and battery packs |
| CN102800864A (en) * | 2012-08-23 | 2012-11-28 | 雅安世佳微尔科技有限公司 | Iron-lithium nanocomposite material synthesis technology |
| CN102916179A (en) * | 2012-09-29 | 2013-02-06 | 杭州金马能源科技有限公司 | Method for manufacturing industrialized high-energy lithium iron phosphate material |
| US8883356B2 (en) | 2008-07-30 | 2014-11-11 | Byd Company Limited | Electrolyte for lithium batteries |
| CN107275638A (en) * | 2017-06-21 | 2017-10-20 | 江苏财经职业技术学院 | Nano-grade lithium iron phosphate composite material and preparation method thereof based on solvent-thermal method |
| CN114644329A (en) * | 2022-04-12 | 2022-06-21 | 深圳沃伦特新能源科技有限公司 | Hydrothermal synthesis method of nano lithium ferric manganese phosphate |
| CN115956134A (en) * | 2020-06-04 | 2023-04-11 | 雅宝德国有限责任公司 | Process for making lithium metal and lithium alloy moldings |
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2005
- 2005-09-16 CN CNB2005100297254A patent/CN100570930C/en active Active
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7722848B2 (en) | 2007-09-25 | 2010-05-25 | Byd Company Limited | Lithium iron phosphate cathode material |
| US8216725B2 (en) | 2008-01-25 | 2012-07-10 | Byd Company Limited | Electrolyte for batteries and battery packs |
| US8088305B2 (en) | 2008-02-22 | 2012-01-03 | Byd Company Limited | Lithium iron phosphate cathode material |
| US8052897B2 (en) | 2008-02-29 | 2011-11-08 | Byd Company Limited | Composite compound with mixed crystalline structure |
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| US8062560B2 (en) | 2008-02-29 | 2011-11-22 | Byd Company Limited | Composite compound with mixed crystalline structure |
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| CN102800864A (en) * | 2012-08-23 | 2012-11-28 | 雅安世佳微尔科技有限公司 | Iron-lithium nanocomposite material synthesis technology |
| CN102916179A (en) * | 2012-09-29 | 2013-02-06 | 杭州金马能源科技有限公司 | Method for manufacturing industrialized high-energy lithium iron phosphate material |
| CN102916179B (en) * | 2012-09-29 | 2015-02-11 | 杭州金马能源科技有限公司 | Method for manufacturing industrialized high-energy lithium iron phosphate material |
| CN107275638A (en) * | 2017-06-21 | 2017-10-20 | 江苏财经职业技术学院 | Nano-grade lithium iron phosphate composite material and preparation method thereof based on solvent-thermal method |
| CN115956134A (en) * | 2020-06-04 | 2023-04-11 | 雅宝德国有限责任公司 | Process for making lithium metal and lithium alloy moldings |
| CN114644329A (en) * | 2022-04-12 | 2022-06-21 | 深圳沃伦特新能源科技有限公司 | Hydrothermal synthesis method of nano lithium ferric manganese phosphate |
| CN114644329B (en) * | 2022-04-12 | 2023-07-07 | 深圳市沃伦特新能源有限公司 | Hydrothermal synthesis method of nano lithium iron manganese phosphate |
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