CN103208627A - Ferric phosphate material and manufacturing method thereof - Google Patents
Ferric phosphate material and manufacturing method thereof Download PDFInfo
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- CN103208627A CN103208627A CN2013100579876A CN201310057987A CN103208627A CN 103208627 A CN103208627 A CN 103208627A CN 2013100579876 A CN2013100579876 A CN 2013100579876A CN 201310057987 A CN201310057987 A CN 201310057987A CN 103208627 A CN103208627 A CN 103208627A
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 76
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000005955 Ferric phosphate Substances 0.000 title abstract description 7
- 229940032958 ferric phosphate Drugs 0.000 title abstract description 7
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 91
- 239000000654 additive Substances 0.000 claims description 74
- 230000000996 additive effect Effects 0.000 claims description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- 229910052742 iron Inorganic materials 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000006232 furnace black Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 9
- 229910052493 LiFePO4 Inorganic materials 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000006245 Carbon black Super-P Substances 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 229910004764 HSV900 Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 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 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- -1 play peptizaiton Chemical compound 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a ferric phosphate material with a porous structure and average pore size of 5-50nm. At the same time, the invention also discloses a preparation method of the ferric phosphate material. A lithium iron phosphate material prepared from the ferric phosphate material provided by the invention has good low temperature and rate performance.
Description
Technical field
The present invention relates to a kind of ferric orthophosphate material and preparation method thereof, especially a kind of ferric orthophosphate material for the preparation of lithium iron phosphate positive material and preparation method thereof.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, have the voltage height, numerous advantages such as energy density is big, the life-span is long, self discharge is little, memory-less effect, operating temperature range are wide, all have a wide range of applications at small-sized mobile energy field (for example mobile phone, digital camera etc.), large-scale mobile energy field (for example plug-in hybrid car, pure electric vehicle etc.) and fixed sources of energy field (for example energy-accumulating power station, UPS etc.).
Positive electrode is the important component part of lithium ion battery, and its performance has determined the combination property of battery to a great extent.Positive electrode research and improvement are one of cores of lithium ion battery development.Positive electrode commonly used has LiCoO
2, LiNiO
2, LiMn
2O
4, LiFePO
4And their derived material.
The LiCoO of layer structure
2, LiNiO
2Perhaps their derivative or large-scale commercial use, combination property is better, but shortcoming such as that it exists is expensive, toxicity is big, thermal stability is low, the basic reserves of raw material are low.The LiMn of spinel structure
2O
4Cost is low, and fail safe is good.But cycle performance, particularly the high humidity cycle performance is relatively poor.In general, the LiFePO4 (LiFePO of olivine structural
4) positive electrode become the domestic and international research focus.
When the preparation LiFePO4, adopt ferric orthophosphate (FePO usually
4.xH
2O
4) as precursor.Therefore, the presoma ferric orthophosphate has considerable influence to the performance of the LiFePO4 of final preparation.
The ferric orthophosphate that prepared in various methods of the prior art obtains is during for the preparation of LiFePO4, and low temperature and the multiplying power discharging property of LiFePO4 are relatively poor.
Summary of the invention
When overcoming ferric orthophosphate of the prior art for the preparation of LiFePO4, the problem of low temperature and high rate performance difference.
The invention provides a kind of ferric orthophosphate material, described ferric orthophosphate material is loose structure, and its average pore size is 5-50nm.
Simultaneously, the invention also discloses above-mentioned ferric orthophosphate preparation methods, comprising:
S1, additive is mixed with water, obtain additive slurry; Described additive is selected from one or more in acetylene black, furnace black, the graphite;
S2, under sour environment, additive slurry is mixed with phosphorus source, source of iron and water, obtain suspension; Described phosphorus source and source of iron are water-soluble; In the described suspension, iron is with Fe
3+Form exists;
S3, under stirring, add in the container suspension and alkali lye are parallel, and the pH value of mixture obtains reaction paste less than 7 in the control container;
S4, reaction paste is carried out Separation of Solid and Liquid, obtain solid precursor material;
S5, precursor material is heat-treated, remove additive, obtain the ferric orthophosphate material.
The inventor finds, what existing ferric orthophosphate preparation method obtained all is full particle, the specific area of the LiFePO4 for preparing of full particle is little thus, when being used for lithium ion battery, lithium ion diffusion length is long, be unfavorable for the infiltration of electrolyte and the quick conduction of lithium ion, thereby cause low temperature and high rate performance relatively poor.
Ferric orthophosphate material disclosed by the invention is loose structure, has bigger specific area and smaller particle size.Adopt the lithium iron phosphate positive material of this ferric orthophosphate material preparation to have bigger specific area, shortened the diffusion length of lithium ion, thereby improved low temperature and the high rate performance of target product.
Concrete, when the present invention prepares the ferric orthophosphate material of above-mentioned porous, form additive slurry earlier, prepare the ferric orthophosphate precursor material with coprecipitation then, heat-treat again and obtain the ferric orthophosphate material.
The inventor finds that in the prior art, the organic materials such as polyethylene glycol that adopt during the preparation ferric orthophosphate mainly play peptizaiton, and its surperficial ferric orthophosphate that is distributed in the ferric orthophosphate for preparing can't serve as that nuclear carries out heterogeneous nucleation with it, and further growth.Thereby the ferric orthophosphate material that obtains is solid construction.Among the present invention, in having the environment of additive, obtain ferric orthophosphate by reaction, ferric orthophosphate can be that nuclear is grown with the additive, and forming with the additive is nuclear, and ferric orthophosphate is the nucleocapsid structure of shell.In follow-up heat treatment process, remove additive, can form the ferric orthophosphate material of porous.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
Ferric orthophosphate material disclosed by the invention is loose structure, and its average pore size is 5-50nm.
Under the preferable case, the average grain diameter of ferric orthophosphate material is 0.5-5 μ m, and specific area is 20-40m
2/ g.
The ferric orthophosphate material of said structure can prepare by the following method:
S1, additive is mixed with water, obtain additive slurry; Described additive is selected from one or more in acetylene black, furnace black, the graphite;
S2, under sour environment, additive slurry is mixed with phosphorus source, source of iron and water, obtain suspension; Described phosphorus source and source of iron are water-soluble; In the described suspension, iron is with Fe
3+Form exists;
S3, under stirring, add in the container suspension and alkali lye are parallel, and the pH value of mixture obtains reaction paste less than 7 in the control container;
S4, reaction paste is carried out Separation of Solid and Liquid, obtain solid precursor material;
S5, precursor material is heat-treated, remove additive, obtain the ferric orthophosphate material.
Among the present invention, the additive of employing is solid material, and can remove by heat treatment.On concrete, above-mentioned additive is selected from acetylene black, furnace black, graphite etc. can be converted into one or more of the nano particle that can volatilize under gaseous volatilization or the air atmosphere with air reaction.As known to those skilled in the art, there is certain uncertainty in chemical reaction, follow-up when removing additive, and the certain residual additive of existence more or less.Above-mentioned residual solid carbon meterial additive can play the effect of conductive agent to a certain extent, when adopting this ferric orthophosphate material further to prepare LiFePO 4 material, is beneficial to and improves its conductivity.The purpose that it should be noted that the step S5 in the inventive method is to remove additive, but residual additive can't cause can not implementing of the inventive method, and the ferric orthophosphate material that obtains by method for preparing still can reach effect of the present invention.
Because the additive that the present invention adopts is solid matter, need earlier additive to be mixed to form additive slurry.Additive can evenly be disperseed, guarantee carrying out smoothly of subsequent reactions process.
Under the preferable case, in the additive slurry, the particle diameter of additive is below the 20nm.At this moment, in the additive slurry, additive can exist with the state of suspended matter, avoids the sedimentation of additive to assemble, and can guarantee follow-up homogeneous reaction to a certain extent.At this moment, in the additive slurry, the weight ratio of additive and water is 1:1-100.But this moment the additive stable existence in the additive slurry.
Form the method for above-mentioned additive slurry without limits, for example, can obtain particle diameter is the following additive of 20nm, then additive is mixed with water.Perhaps, additive is mixed with water, then additive is ground to below the 20nm.
According to the present invention, among the step S2, need additive slurry is mixed with phosphorus source, source of iron and water, form suspension.Wherein, phosphorus source and source of iron are water-soluble.Form the accessory substance precipitation for fear of water-soluble phosphorus source and source of iron, so above-mentioned being blended under the acid condition carried out.Concrete, can add a certain amount of acid solution simultaneously.
Above-mentioned phosphorus source is selected from one or more in phosphoric acid, dihydric phosphate, the orthophosphates.Under the preferable case, can directly adopt phosphoric acid to form sour environment.
In the suspension described above, iron is with Fe
3+Form exists.Concrete, described source of iron can directly adopt ferric iron source.For example, ferric iron source can be selected from one or more in ferric sulfate, ferric nitrate, iron chloride, the primary iron phosphate.
Simultaneously, when adding source of iron, can adopt the mixture of divalence source of iron or divalence source of iron and ferric iron source.Be to contain the divalence source of iron in the source of iron.At this moment, need be ferric iron with oxidation of divalent, make its in suspension with Fe
3+Form exists.
Above-mentioned oxidation treatment method is for existing, for example, with additive slurry with after phosphorus source, source of iron and water mix, aerating oxygen or air 2-10h.
Perhaps additive slurry, phosphorus source, source of iron, water and oxidant are mixed, by oxidant with the oxidation of divalence source of iron.
Concrete, described oxidant is selected from one or more in hydrogen peroxide, nitric acid, nitrate, potassium permanganate, potassium bichromate, the sodium peroxide.
The addition of above-mentioned oxidant is to be that ferric iron is as the criterion with the oxidation of divalent in the divalence source of iron, and concrete addition is that those skilled in the art add according to actual conditions, can be excessive.Under the preferable case, described oxidant is than the excessive 10-100% of theoretical aequum;
Above-mentioned phosphorus source and source of iron are as the raw material of reaction generation ferric orthophosphate, and its addition is for well known to a person skilled in the art, for example, in the molal quantity of P elements and ferro element, the ratio of the addition of phosphorus source and source of iron is 1-3:1.
Among the described step S2, when additive slurry was mixed with phosphorus source, source of iron and water, the weight ratio of additive and source of iron was 0.001-1:1.
According to the present invention, step S3 is coprecipitation reaction, generates ferric orthophosphate.Among the present invention, the condition of step S3 does not have specific (special) requirements, can adopt existence conditions, and for example, under stirring, in suspension and the parallel adding of alkali lye container, and the pH value of controlling mixture in the container obtains reaction paste less than 7.
Under the preferable case, the pH value of mixture remains on 2-2.5 in the control container; After described suspension and alkali lye interpolation are finished, continue to stir 1-2h.
Wherein, alkali lye is selected from one or more in sodium hydroxide solution, potassium hydroxide solution, the ammoniacal liquor.
The inventor finds, if adding additive again after reaction generates ferric orthophosphate (or directly adopting ferric orthophosphate) heat-treats, then additive only is present in the ferric orthophosphate surface, even by heat treatment, also the ironing surface additive of orthophosphoric acid can only be removed, can't form the ferric orthophosphate structure of porous.
Among the present invention, form suspension by earlier additive slurry being mixed with phosphorus source, source of iron and water, carry out coprecipitation reaction then.Be reflected in the environment that additive exists and carry out.Obtain ferric orthophosphate by reaction, ferric orthophosphate can be that nuclear is grown with the additive, and forming with the additive is nuclear, and ferric orthophosphate is the nucleocapsid structure of shell.
After coprecipitation reaction finished, the reaction paste that needs reaction is obtained carried out Separation of Solid and Liquid, obtains solid-state precursor material.As known in the art, when obtaining precursor material, be washed to neutrality usually, dry then.
According to the present invention, among the step S5, need precursor material is heat-treated, remove additive, obtain the ferric orthophosphate material.
Above-mentioned heat treatment method purpose is for removing additive, and concrete grammar is that this area is commonly used, for example, in air or oxygen atmosphere, keeps 1-24h down in 400-800 ℃.
Can obtain the ferric orthophosphate material of porous by said method disclosed by the invention, its average pore size is 5-50nm.
By the following examples the present invention is further detailed.
Embodiment 1
Present embodiment is used for explanation ferric orthophosphate material disclosed by the invention and preparation method thereof.
Take by weighing acetylene black 5g, deionized water 200g is with the two mixing, with sand mill (Bu Le, MicroMedia
TM) acetylene black is ground to below the 20nm, form additive slurry.
Add the 268.5g mass fraction in the additive slurry and be 73% industrial phosphoric acid, the mass fraction that adds 275.2g iron is 20.29% technical grade green vitriol, adding 57g mass fraction is 30% technical grade hydrogen peroxide, add water and be settled to 1L, and fully stirring makes ferrous iron all be oxidized to ferric iron, obtains suspension.
Add the 600g deionized water in the reactor of 4L liner PE, opening electric heater is 50 ℃ until reaction system, constant temperature.In 4h, by measuring pump suspension is at the uniform velocity added reactor, accordingly, feedback signal control measuring pump by placing the PH electrode in the reactor continues to add the sodium hydroxide solution of 5M in the reactor, keeps that pH value is 2.3 ± 0.03 in the entire reaction course.After reaction finishes, continue to stir 1h.Obtain reaction paste.
With the vacuum filtration device reaction paste is carried out Separation of Solid and Liquid, obtain the grey filter cake, with filter cake and 1000g deionized water mixing agitator treating, and carry out Separation of Solid and Liquid.Triplicate, 120 ℃ of oven dry obtain precursor material.Determine that by XRD precursor material is the ferric orthophosphate that contains carbon.Analysis of carbon and sulfur shows and wherein contains 3.2% carbon.
Precursor material under air atmosphere, is handled 6h for 500 ℃, obtain the ferric orthophosphate material of yellow-white.Its specific area is 32.6m
2/ g, average grain diameter is 2.8 μ m, average pore size is 12nm.
Analysis of carbon and sulfur shows and wherein contains 0.1% carbon that namely most of acetylene black is removed.
With ferric orthophosphate material and battery-level lithium carbonate micro mist according to the iron lithium than being the mixed in molar ratio of 1:1, and add the glucose that is equivalent to ferric phosphate mass fraction 20%, add appropriate amount of deionized water, grind.120 ℃ of oven dry then.Under nitrogen atmosphere, handle 5h for 700 ℃ again, obtain the carbon-coated LiFePO 4 for lithium ion batteries of grey black, its specific area is 21.3m
2/ g.
Above-mentioned carbon-coated LiFePO 4 for lithium ion batteries material is mixed according to the mass ratio of 100:5:5 with super-P (Merk), pvdf (A Ke sign indicating number HSV900), as positive pole.As negative pole, make the smear button cell with the lithium sheet.
At 2.5-3.8V, under normal temperature (23 ℃) 0.5C, recording battery gram specific capacity is 155mAh/g.
At 2.5-3.8V, under normal temperature (23 ℃) 5C, recording battery gram specific capacity is 145mAh/g.
At 2.0-3.8V ,-10 ℃, under the 0.5C, recording battery gram specific capacity is 116mAh/g.
Be that normal temperature discharge 5C/0.5C ratio is 93.5%.
Low temperature discharge-10 ℃/23 ℃ of ratios are 74.8%.
Embodiment 2
Present embodiment is used for explanation ferric orthophosphate material disclosed by the invention and preparation method thereof.
Take by weighing furnace black 2g, deionized water 80g is with the two mixing, with sand mill (Bu Le, MicroMedia
TM) furnace black is ground to below the 20nm, form additive slurry.
Add the 335.6g mass fraction in the additive slurry and be 73% industrial phosphoric acid, the mass fraction that adds 137.6g iron is that the mass fraction of 20.29% technical grade green vitriol and 100g iron is 27.92% technical grade four Ferric Chloride Hydrateds, feeds compressed air 10h.Add water and be settled to 1L, and fully stirring makes ferrous iron all be oxidized to ferric iron, obtains suspension.
Add the 600g deionized water in the reactor of 4L liner PE, opening electric heater is 50 ℃ until reaction system, constant temperature.In 4h, by measuring pump suspension is at the uniform velocity added reactor, accordingly, feedback signal control measuring pump by placing the PH electrode in the reactor continues to add the sodium hydroxide solution of 5M in the reactor, keeps that pH value is 2.3 ± 0.03 in the entire reaction course.After reaction finishes, continue to stir 1h.Obtain reaction paste.
With the vacuum filtration device reaction paste is carried out Separation of Solid and Liquid, obtain the grey filter cake, with filter cake and 1000g deionized water mixing agitator treating, and carry out Separation of Solid and Liquid.Triplicate, 120 ℃ of oven dry obtain precursor material.Determine that by XRD precursor material is the ferric orthophosphate that contains carbon.Analysis of carbon and sulfur shows and wherein contains 1.42% carbon.
Precursor material under air atmosphere, is handled 2h for 600 ℃, obtain the ferric orthophosphate material of yellow-white.Its specific area is 26.3m
2/ g, average grain diameter is 2.2 μ m, average pore size is 18nm.
Analysis of carbon and sulfur shows and wherein contains 0.05% carbon that namely most of furnace black is removed.
With ferric orthophosphate material and battery-level lithium carbonate micro mist according to the iron lithium than being the mixed in molar ratio of 1:1, and add the glucose that is equivalent to ferric phosphate mass fraction 20%, add appropriate amount of deionized water, grind.120 ℃ of oven dry then.Under nitrogen atmosphere, handle 5h for 700 ℃ again, obtain the carbon-coated LiFePO 4 for lithium ion batteries of grey black, its specific area is 18.7m
2/ g.
Above-mentioned carbon-coated LiFePO 4 for lithium ion batteries material is mixed according to the mass ratio of 100:5:5 with super-P (Merk), pvdf (A Ke sign indicating number HSV900), as positive pole.As negative pole, make the smear button cell with the lithium sheet.
At 2.5-3.8V, under normal temperature (23 ℃) 0.5C, recording battery gram specific capacity is 153mAh/g.
At 2.5-3.8V, under normal temperature (23 ℃) 5C, recording battery gram specific capacity is 141mAh/g.
At 2.0-3.8V ,-10 ℃, under the 0.5C, recording battery gram specific capacity is 113mAh/g.
Be that normal temperature discharge 5C/0.5C ratio is 92.2%.
Low temperature discharge-10 ℃/23 ℃ of ratios are 73.9%.
Embodiment 3
Present embodiment is used for explanation ferric orthophosphate material disclosed by the invention and preparation method thereof.
Take by weighing acetylene black 10g, deionized water 400g is with the two mixing, with sand mill (Bu Le, MicroMedia
TM) acetylene black is ground to below the 20nm, form additive slurry.
Add the 402.7g mass fraction in the additive slurry and be 73% industrial phosphoric acid, the mass fraction that adds 200g iron is 27.92% technical grade four Ferric Chloride Hydrateds, feeds compressed air 24h.Add water and be settled to 1L, and fully stirring makes ferrous iron all be oxidized to ferric iron, obtains suspension.Stir, obtain suspension.
Add the 600g deionized water in the reactor of 4L liner PE, opening electric heater is 50 ℃ until reaction system, constant temperature.In 4h, by measuring pump suspension is at the uniform velocity added reactor, accordingly, feedback signal control measuring pump by placing the PH electrode in the reactor continues to add the sodium hydroxide solution of 5M in the reactor, keeps that pH value is 2.3 ± 0.03 in the entire reaction course.After reaction finishes, continue to stir 1h.Obtain reaction paste.
With the vacuum filtration device reaction paste is carried out Separation of Solid and Liquid, obtain the grey filter cake, with filter cake and 1000g deionized water mixing agitator treating, and carry out Separation of Solid and Liquid.Triplicate, 120 ℃ of oven dry obtain precursor material.Determine that by XRD precursor material is the ferric orthophosphate that contains carbon.Analysis of carbon and sulfur shows and wherein contains 7.83% carbon.
Precursor material under air atmosphere, is handled 5h for 700 ℃, obtain the ferric orthophosphate material of yellow-white.Its specific area is 38.2m
2/ g, average grain diameter is 1.9 μ m, average pore size is 24nm.
Analysis of carbon and sulfur shows and wherein contains 0.07% carbon that namely most of acetylene black is removed.
With ferric orthophosphate material and battery-level lithium carbonate micro mist according to the iron lithium than being the mixed in molar ratio of 1:1, and add the glucose that is equivalent to ferric phosphate mass fraction 20%, add appropriate amount of deionized water, grind.120 ℃ of oven dry then.Under nitrogen atmosphere, handle 5h for 700 ℃ again, obtain the carbon-coated LiFePO 4 for lithium ion batteries of grey black, its specific area is 25.8m
2/ g.
Above-mentioned carbon-coated LiFePO 4 for lithium ion batteries material is mixed according to the mass ratio of 100:5:5 with super-P (Merk), pvdf (A Ke sign indicating number HSV900), as positive pole.As negative pole, make the smear button cell with the lithium sheet.
At 2.5-3.8V, under normal temperature (23 ℃) 0.5C, recording battery gram specific capacity is 156mAh/g.
At 2.5-3.8V, under normal temperature (23 ℃) 5C, recording battery gram specific capacity is 147mAh/g.
At 2.0-3.8V ,-10 ℃, under the 0.5C, recording battery gram specific capacity is 118mAh/g.
Be that normal temperature discharge 5C/0.5C ratio is 94.2%.
Low temperature discharge-10 ℃/23 ℃ of ratios are 75.6%.
Comparative Examples 1
This Comparative Examples is used for comparative illustration ferric orthophosphate material disclosed by the invention.
Adopt embodiment 1 described method to prepare the ferric orthophosphate material, different is not add additive slurry.
The specific area that obtains the ferric orthophosphate material is 12.1m
2/ g.
At 2.5-3.8V, under normal temperature (23 ℃) 0.5C, recording battery gram specific capacity is 154mAh/g.
At 2.5-3.8V, under normal temperature (23 ℃) C, recording battery gram specific capacity is 136mAh/g.
At 2.0-3.8V ,-10 ℃, under the 0.5C, recording battery gram specific capacity is 95mAh/g.
Be that normal temperature discharge 5C/0.5C ratio is 88.3%.
Low temperature discharge-10 ℃/23 ℃ of ratios are 61.7%.
Comparative Examples 2
This Comparative Examples is used for comparative illustration ferric orthophosphate material disclosed by the invention.
Adopt embodiment 1 described method to prepare the ferric orthophosphate material, different is to substitute additive slurry with polyethylene glycol.
The specific area that obtains the ferric orthophosphate material is 14.5m
2/ g.
At 2.5-3.8V, under normal temperature (23 ℃) 0.5C, recording battery gram specific capacity is 155mAh/g.
At 2.5-3.8V, under normal temperature (23 ℃) C, recording battery gram specific capacity is 137mAh/g.
At 2.0-3.8V ,-10 ℃, under the 0.5C, recording battery gram specific capacity is 97mAh/g.
Be that normal temperature discharge 5C/0.5C ratio is 88.4%.
Low temperature discharge-10 ℃/23 ℃ of ratios are 62.6%.
The test result of comparative example 1 and Comparative Examples 1 as can be known, after the ferric orthophosphate material for preparing by method disclosed by the invention further prepares LiFePO 4 material, the obvious raising that the low temperature of the battery of its formation and high rate performance obtain.
The test result of comparative example 1 and Comparative Examples 2 adopts existing organic substance as can be known, organic carbon source such as polyethylene glycol for example, and low temperature and the high rate performance of the battery that the ferric orthophosphate material for preparing further forms are still lower.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (11)
1. a ferric orthophosphate material is characterized in that, described ferric orthophosphate material is loose structure, and its average pore size is 5-50nm.
2. ferric orthophosphate material according to claim 1 is characterized in that, the average grain diameter of described ferric orthophosphate material is 0.5-5 μ m, and specific area is 20-40m
2/ g.
3. ferric orthophosphate preparation methods as claimed in claim 1 or 2 comprises:
S1, additive is mixed with water, obtain additive slurry; Described additive is selected from one or more in acetylene black, furnace black, the graphite;
S2, under sour environment, additive slurry is mixed with phosphorus source, source of iron and water, obtain suspension; Described phosphorus source and source of iron are water-soluble; In the described suspension, iron is with Fe
3+Form exists;
S3, under stirring, add in the container suspension and alkali lye are parallel, and the pH value of mixture obtains reaction paste less than 7 in the control container;
S4, reaction paste is carried out Separation of Solid and Liquid, obtain solid precursor material;
S5, precursor material is heat-treated, remove additive, obtain the ferric orthophosphate material.
4. preparation method according to claim 3 is characterized in that, among the described step S1, additive mixes by the weight ratio of 1:1-100 with water;
The particle diameter of additive is below the 20nm in the additive slurry.
5. preparation method according to claim 3 is characterized in that, among the described step S2, the phosphorus source is selected from one or more in phosphoric acid, dihydric phosphate, the orthophosphates; Described source of iron is ferric iron source.
6. preparation method according to claim 3 is characterized in that, among the described step S2, the phosphorus source is selected from one or more in phosphoric acid, dihydric phosphate, the orthophosphates; Described source of iron is the mixture of divalence source of iron or divalence source of iron and ferric iron source;
Also comprise among the described step S3 ferrous iron in the described divalence source of iron is carried out oxidation processes, obtain suspension.
7. preparation method according to claim 6 is characterized in that, described oxidation processes is: with additive slurry with after phosphorus source, source of iron and water mix, aerating oxygen or air 2-10h;
Perhaps additive slurry, phosphorus source, source of iron, water and oxidant are mixed; Described oxidant is more excessive slightly than known mol ratio with the divalence source of iron; Described oxidant is selected from one or more in hydrogen peroxide, nitric acid, nitrate, potassium permanganate, potassium bichromate, the sodium peroxide.
8. according to any described preparation method among the claim 4-7, it is characterized in that among the described step S2, when additive slurry was mixed with phosphorus source, source of iron and water, the weight ratio of additive and source of iron was 0.001-1:1;
In the molal quantity of P elements and ferro element, the ratio of the addition of phosphorus source and source of iron is 1-3:1.
9. preparation method according to claim 3 is characterized in that, among the described step S3, the pH value of mixture remains on 2-2.5 in the control container; After described suspension and alkali lye interpolation are finished, continue to stir 1-2h.
10. preparation method according to claim 9 is characterized in that, described alkali lye is selected from one or more in sodium hydroxide solution, potassium hydroxide solution, the ammoniacal liquor.
11. according to any described preparation method among the claim 4-7,9,10, it is characterized in that among the described step S5, heat-treating methods is: in air or oxygen atmosphere, keep 1-24h down in 400-800 ℃.
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| CN110182779A (en) * | 2019-05-07 | 2019-08-30 | 湖南雅城新材料有限公司 | The preparation method of ferric phosphate duct material |
| CN113292059A (en) * | 2021-05-18 | 2021-08-24 | 江苏锂源电池材料有限公司 | Preparation method for improving multiplying power of lithium iron phosphate by changing iron phosphate pores |
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| CN108557794A (en) * | 2018-04-28 | 2018-09-21 | 贵州贵航新能源科技有限公司 | A kind of preparation method of porous calcium phosphate iron nano powder |
| CN110182779A (en) * | 2019-05-07 | 2019-08-30 | 湖南雅城新材料有限公司 | The preparation method of ferric phosphate duct material |
| CN113292059A (en) * | 2021-05-18 | 2021-08-24 | 江苏锂源电池材料有限公司 | Preparation method for improving multiplying power of lithium iron phosphate by changing iron phosphate pores |
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