CN108455553A - Cellular ferric phosphate and preparation method thereof and LiFePO4 - Google Patents
Cellular ferric phosphate and preparation method thereof and LiFePO4 Download PDFInfo
- Publication number
- CN108455553A CN108455553A CN201810219369.XA CN201810219369A CN108455553A CN 108455553 A CN108455553 A CN 108455553A CN 201810219369 A CN201810219369 A CN 201810219369A CN 108455553 A CN108455553 A CN 108455553A
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- Prior art keywords
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- phosphate
- porous material
- ferric phosphate
- organic porous
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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 55
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 54
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 53
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000001413 cellular effect Effects 0.000 title claims abstract description 25
- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011148 porous material Substances 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 22
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000006210 lotion Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 18
- 239000010452 phosphate Substances 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 238000011085 pressure filtration Methods 0.000 claims abstract description 12
- 238000010790 dilution Methods 0.000 claims abstract description 11
- 239000012895 dilution Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- -1 iron ion Chemical class 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000011343 solid material Substances 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000007812 deficiency Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000009415 formwork Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 102100034213 ATPase family protein 2 homolog Human genes 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 108010091193 spermatogenesis associated factor Proteins 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 101000983970 Conus catus Alpha-conotoxin CIB Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to battery material field, discloses a kind of cellular ferric phosphate and preparation method thereof and LiFePO4, the preparation method include：Lotion containing organic porous material, the solution containing molysite and the solution containing phosphate radical are mixed, obtained mixed emulsion is contacted with oxidant, slurry will be obtained after product pressure filtration washing after contact, ageing is contacted after the pulp dilution with phosphoric acid, high temperature sintering is carried out to the solid material obtained after ageing.This method obviates the deficiencies of hard aggregation that current ferric phosphate production process occurs；Also, different-shape and the ferric phosphate of size can be realized by organic formwork early period, reduce the influence of later crystallization temperature, material concentration, terminal pH to finished product；In addition, the LiFePO4 prepared by the cellular ferric phosphate inherits honeycomb, can electrolyte be come into full contact with it, lithium ion diffusion path shortens, to significantly improve the multiplying power and cryogenic property of material.
Description
Technical field
The present invention relates to battery material fields, and in particular to a kind of preparation method of cellular ferric phosphate, the preparation method
Obtained cellular ferric phosphate and the LiFePO4 being prepared by cellular ferric phosphate.
Background technology
Ferric phosphate, molecular formula FePO4, it is a kind of typical phosphate, is used primarily for the row such as food additives, coating
Industry becomes mainstream, the synthesis of ferric phosphate with the development of battery material LiFePO4 by the synthetic route of presoma of ferric phosphate
Technology and market all achieved rapid progress at nearly 5 years.
The synthesis technology of ferric phosphate by improving for many years, focal point how much turned to its structure by contained heavy metal and
The concern of granule-morphology, these parameters can influence the performance of follow-up LiFePO4.Current ferric phosphate synthesis technology, substantially flow are
Solution crystallization, washing, filtering, sintering finally obtain finished product, and the reunion of gained ferric phosphate is serious, when subsequently being reacted with lithium carbonate, lithium
The path length when high temperature solid-state is spread, product particle is big, and corresponding LiFePO4 multiplying power and low temperature performance decline.
Invention content
It is serious the purpose of the invention is to overcome the ferric phosphate that existing ferric phosphate preparation method prepares to reunite, and
The bad problem of the multiplying power and low temperature performance of LiFePO4 prepared therefrom provides a kind of cellular ferric phosphate and its preparation
Method and LiFePO4.
To achieve the goals above, one aspect of the present invention provides the preparation method of cellular ferric phosphate, wherein the preparation side
Method includes：Lotion containing organic porous material, the solution containing molysite and the solution containing phosphate radical are mixed, what is obtained is mixed
It closes lotion to contact with oxidant, slurry will be obtained after the product pressure filtration washing after contact, contacted with phosphoric acid after the pulp dilution
Ageing carries out high temperature sintering to the solid material obtained after ageing.
Second aspect of the present invention provides the cellular ferric phosphate being prepared by the preparation method of the present invention.
Third aspect present invention provides a kind of LiFePO4, wherein the LiFePO4 is by the raw material system containing ferric phosphate
At the ferric phosphate is the cellular ferric phosphate of the present invention.
The method of the present invention provides the template of ferric phosphate crystallization by organic porous material, the crystallization shape for making hardly possible controllable
The deficiencies of being designed before start, obviating the hard aggregation that current ferric phosphate production process occurs；Also, different-shape and big
Small ferric phosphate can be realized by organic formwork early period, reduce later crystallization temperature, material concentration, terminal pH to finished product
Influence；In addition, the cellular ferric phosphate inherits honeycomb with lithium source LiFePO4 obtained by the reaction, can be electrolysed
Liquid comes into full contact with it, and lithium ion diffusion path shortens, to significantly improve the multiplying power and cryogenic property of material.
Description of the drawings
Fig. 1 is the SEM figures of the cellular ferric phosphate of the present invention.
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of preparation method of cellular ferric phosphate, wherein the preparation method includes：It will contain
There are lotion, the solution containing molysite and the mixing of the solution containing phosphate radical of organic porous material, obtained mixed emulsion and oxygen
Agent contacts, and slurry will be obtained after the product pressure filtration washing after contact, ageing is contacted with phosphoric acid after the pulp dilution, to ageing
The solid material obtained afterwards carries out high temperature sintering.
Organic porous material, the hole of organic porous material is added in the method for the invention in the raw material for preparing ferric phosphate
Space is provided for the growth of form iron phosphate crystal, high temperature sintering, organic matter decompose oxidation, obtain cellular crystal development again after the completion
Ferric phosphate, as shown in Figure 1.
In the present invention, the organic porous material can be it is existing there is cavernous structure and high temperature sintering after can decompose
Organic material, the aperture of the organic porous material can be selected according to the honeycomb of target product ferric phosphate, be
Charge-discharge performance when raising cellular ferric phosphate is applied in the battery, it is preferable that the organic porous material has for macropore
At least one of machine porous material, mesoporous organic porous material and micropore organic porous material；It is further preferred that described have
The aperture of machine porous material is 10-150nm, preferably 20-110nm, further preferably 30-80nm.
In the present invention, to the solid content of the lotion containing organic porous material, there is no particular limitation, it is preferable that
In the lotion containing organic porous material, the content of the organic porous material is 8-30 weight %.
In the present invention, also contain surfactant in the lotion containing organic porous material.
In the present invention, to the concentration of the solution containing molysite, there is no particular limitation, it is preferable that described containing molysite
In solution, a concentration of 0.6-2mol/L of the molysite, further preferably 0.8-1.5mol/L；The solution containing molysite
It can be the aqueous solution containing molysite.
In the present invention, the molysite can be the existing molysite that can be used in preparing ferric phosphate, for example, the molysite is can
Dissolubility ferrous salt；Specifically, the molysite can be ferrous sulfate and/or frerrous chloride.
In the present invention, in the solution containing phosphate radical, the concentration of phosphate radical is preferably 0.6-2mol/L, further
Preferably 0.8-1.3mol/L；The solution of the phosphorous acid group can be the aqueous solution of phosphoric acid root.
In the present invention, the phosphate radical can be by providing, for example, the phosphorus containing phosphate radical and with soluble substance
Acid group is provided by least one of phosphoric acid, ammonium phosphate salt, ammonium hydrogen phosphate, sodium phosphate and dibastic sodium phosphate.
In the present invention, it is preferable that in the iron ion and the solution containing phosphate radical in the solution containing molysite
Phosphate radical dosage molar ratio be 0.98-1.03：1.
In the present invention, it is preferable that the dosage of the organic porous material is the 1-17 weight % of the mixed emulsion, preferably
For 2-10 weight %.
A preferred embodiment of the invention by the lotion containing organic porous material, contains the solution of molysite
With containing phosphate radical solution mixing mode include：First the lotion containing organic porous material and the solution containing molysite are mixed
Uniform stirring 60-180min (preferably 120-150min) is closed, the solution containing phosphate radical is added, is stirred after forming mixed emulsion
Mix 120-240min (preferably 150-200min).
In the present invention, the oxidant can be this field conventional selection, for example, the oxidant be hydrogen peroxide and/
Or hypochlorous acid.The concentration of the oxidant can be 7-25 weight %.
According to another preferred method of implementation of the present invention, the preparation method further includes：Product after it will contact into
Before row pressure filtration washing, the pH of the product after adjusting the contact with lye is 1.6-3.2, preferably 2-2.8.
The present invention, the lye can be this field conventional selection, for example, the lye be ammonium hydroxide, sodium hydroxide and
At least one of potassium hydroxide.
In the present invention, the process of the pressure filtration washing refers to the product of washings docking after touch wash and press repeatedly
Filter, it is preferable that when the conductivity for being press-filtered out the water come for the last time is less than 10000us/cm (preferably smaller than 8000us/cm),
Terminate the pressure filtration washing process.The temperature of the washings is preferably 30-80 DEG C, further preferably 40-70 DEG C.It is described to wash
The volume ratio of the dosage and slurry of washing water can be 2-5：1.
In the present invention, the process of the pulp dilution is diluted using hot water, it is preferable that the temperature of the hot water is 60-95
℃.The dosage for diluting the dilution water used and the volume ratio of slurry is 1-10：1.
In the present invention, the concentration of the phosphoric acid can be 0.5-2mol/L, preferably 0.8-1.5mol/L.The ageing
Time can be 4-10h, preferably 7-8h.The dosage of the phosphoric acid and the volume ratio of slurry after dilution are preferably 0.01-0.05：
1。
In the present invention, it is preferable that the preparation method can also include：After the ageing and the high temperature sintering it
Before, washing and press filtration are carried out to the material obtained after the ageing and slough Free water.The process for sloughing Free water makes
Water content in obtained solid material is 15-30 weight %.The mode for sloughing Free water can be used vacuum drying, dodge
Steaming, spray drying or resistance stove heat.
In the present invention, the temperature of the high temperature sintering is preferably 400-680 DEG C, further preferably 450-640 DEG C.It is described
The process of high temperature sintering can be implemented in rotary kiln, pusher furnace or roller furnace.
Second aspect of the present invention provides the cellular ferric phosphate being prepared by the preparation method of the present invention.
Third aspect present invention provides a kind of LiFePO4, wherein the LiFePO4 is by the raw material system containing ferric phosphate
At the ferric phosphate is the cellular ferric phosphate of the present invention.
In the present invention, for the specific method for preparing LiFePO4, there is no particular limitation, can be commonly used in the art
Various methods, such as can be：It is mixed as presoma, by it with lithium source, carbon source and solvent using the cellular ferric phosphate of the present invention,
Obtain slurry；Slurry is dry, crushing, is then roasted under protective atmosphere.
Wherein, lithium source, carbon source and solvent can be respectively various lithium sources, carbon source and solvent commonly used in the art, for example, lithium
Source can be lithium carbonate, lithium hydroxide, lithium bicarbonate, lithium phosphate, lithium carbonate, lithium acetate, lithium chloride, lithium dihydrogen phosphate, oxalic acid
One or more in lithium and lithium nitrate, carbon source can be in glucose, sucrose, lactose, citric acid, polyethylene glycol and stearic acid
It is one or more, solvent can be deionized water, absolute ethyl alcohol, isopropanol and acetone in it is one or more.
Wherein, the drying can be the mode of this field routine, for example, spray drying.
Wherein, the condition of the roasting may include：Temperature is 700-800 DEG C, time 4-8h.
The present invention will be described in detail by way of examples below.
Embodiment 1
(1) 6000 gram-molecular weights 100,000 are weighed, the organic porous polymer (GPPS, purchased from the U.S. that aperture is 30nm-60nm
The Dow Chemical Company, trade mark 666H), (REASOP is purchased from Japanese strain Shi Hui ADEKA companies, trade mark SE- to 10 grams of surfactants
10) it, is added in 50 liters of glass kettles with double-valve type agitating paddle, then is pumped into 27 liters of deionized waters, pass through external mulser and kettle
Interior agitating paddle, is configured to latex A；
(2) the ferrous sulfate solution B of 10 liters of 0.8mol/L is configured；
(3) the phosphoric acid solution C of 10 liters of 0.8mol/L is configured；
(4) latex A is pumped into 100 liters of the glass reaction kettle with stirring and emulsification, solution B and solution C are simultaneously all with 1L/
The container that the speed of min is pumped into existing latex A obtains new lotion D, emulsifies unit frequency 6HZ, 200 revs/min of mixing speed；
(5) hydrogen peroxide of 2.0 liters of a concentration of 10 weight % is added into lotion D, then pH is adjusted with the ammonium hydroxide of 15 weight %
Terminal obtains suspension E to 2.0；
(6) by 60 DEG C of deionized water washing and filter pressings 3 times of suspension E, last time pressing filtering liquid conductivity is 6540us/
cm；
(7) 2 liters of 0.8mol/L phosphoric acid are added after 35 liters of 70 DEG C of hot water dilutions are added in slurry, and ageing 7 hours are kept the temperature at 70 DEG C；
(8) slurry pressure filtration washing is primary after being aged, then cryogenic vacuum dries to obtain solid powder (water content is 15 weights
Measure %)；
(9) solid powder is sintered in chamber type electric resistance furnace, and sintering temperature is 480 DEG C, and sintering time is 6 hours.Obtain bee
Nest shape ferric phosphate.
Embodiment 2
(1) 2348 gram-molecular weights 200,000 are weighed, the organic porous polymer (SPAF, purchased from the U.S. that aperture is 50nm-80nm
The Dow Chemical Company, trade mark AF-3), (REASOP is purchased from Japanese strain Shi Hui ADEKA companies, trade mark SE- to 5 grams of surfactants
10) it, is added in 50 liters of glass kettles with double-valve type agitating paddle, then is pumped into 27 liters of deionized waters, pass through external mulser and kettle
Interior agitating paddle, is configured to latex A；
(2) the ferrous sulfate solution B of 10 liters of 1.35mol/L is configured；
(3) the phosphoric acid solution C of 10 liters of 1.3mol/L is configured；
(4) latex A is pumped into 100 liters of the glass reaction kettle with stirring and emulsification, solution B and solution C are simultaneously all with 1L/
The container that the speed of min is pumped into existing latex A obtains new lotion D, emulsifies unit frequency 6HZ, 200 revs/min of mixing speed；
(5) hydrogen peroxide of a concentration of 25 weight % of 1.5L is added into lotion D, then pH ends are adjusted with the ammonium hydroxide of 15 weight %
O'clock to 2.8, suspension E is obtained；
(6) by 40 DEG C of deionized water washing and filter pressings 3 times of suspension E, last time pressing filtering liquid conductivity is 6540us/
cm；
(7) 2 liters of 0.8mol/L phosphoric acid are added after 35 liters of 60 DEG C of hot water dilutions are added in slurry, and ageing 7 hours are kept the temperature at 70 DEG C；
(8) slurry pressure filtration washing is primary after being aged, then cryogenic vacuum dries to obtain solid powder (water content is 20 weights
Measure %)；
(9) solid powder is sintered in chamber type electric resistance furnace, and sintering temperature is 450 DEG C, and sintering time is 6 hours.Obtain bee
Nest shape ferric phosphate.
Embodiment 3
(1) 11580 gram-molecular weights 200,000 are weighed, the organic porous polymer (SPAF, purchased from the U.S. that aperture is 40-70nm
The Dow Chemical Company, trade mark AF-7), (REASOP is purchased from Japanese strain Shi Hui ADEKA companies, trade mark SE- to 20 grams of surfactants
10) it, is added in 50 liters of glass kettles with double-valve type agitating paddle, then is pumped into 27 liters of deionized waters, pass through external mulser and kettle
Interior agitating paddle, is configured to latex A；
(2) the ferrous sulfate solution B of 10 liters of 1mol/L is configured；
(3) the phosphoric acid solution C of 10 liters of 1mol/L is configured；
(4) latex A is pumped into 100 liters of the glass reaction kettle with stirring and emulsification, solution B and solution C are simultaneously all with 1L/
The container that the speed of min is pumped into existing latex A obtains new lotion D, emulsifies unit frequency 6HZ, 200 revs/min of mixing speed；
(5) hydrogen peroxide of 2.0 liters of a concentration of 7 weight % is added into lotion D, then pH ends are adjusted with the ammonium hydroxide of 15 weight %
O'clock to 2.8, suspension E is obtained；
(6) by 70 DEG C of deionized water washing and filter pressings 3 times of suspension E, last time pressing filtering liquid conductivity is 5280us/
cm；
(7) 3 liters of 1.5mol/L phosphoric acid are added after 35 liters of 90 DEG C of hot water dilutions are added in slurry, and ageing 8 hours are kept the temperature at 70 DEG C；
(8) slurry pressure filtration washing is primary after being aged, then cryogenic vacuum dries to obtain solid powder (water content is 30 weights
Measure %)；
(9) solid powder is sintered in chamber type electric resistance furnace, and sintering temperature is 640 DEG C, and sintering time is 6 hours.Obtain bee
Nest shape ferric phosphate.
Embodiment 4
Prepare cellular ferric phosphate according to the method for embodiment 1, unlike, the aperture of the organic porous material used for
115-150nm。
Comparative example 1
Cellular ferric phosphate is prepared according to the method for embodiment 1, unlike, any organic porous polymer is not added,
Specially：
(1) the ferrous sulfate solution B of 10 liters of 0.8mol/L is configured；
(2) the phosphoric acid solution C of 10 liters of 0.8mol/L is configured；
(3) solution B and solution C are all pumped into the speed of 1L/min in container simultaneously obtains new lotion D, emulsifies unit frequency
6HZ, 200 revs/min of mixing speed；
(4) hydrogen peroxide of 2.0 liters of a concentration of 10 weight % is added into lotion D, then pH is adjusted with the ammonium hydroxide of 15 weight %
Terminal obtains suspension E to 2.1；
(5) by 60 DEG C of deionized water washing and filter pressings 3 times of suspension E, last time pressing filtering liquid conductivity is 6540us/
cm；
(6) 2 liters of 0.85mol/L phosphoric acid are added after 35 liters of 70 DEG C of hot water dilutions are added in slurry, and heat preservation ageing 6 is small at 70 DEG C
When；
(7) slurry pressure filtration washing is primary after being aged, then cryogenic vacuum dries to obtain solid powder (water content is 15 weights
Measure %)；
(8) solid powder is sintered in chamber type electric resistance furnace, and sintering temperature is 480 DEG C, and sintering time is 6 hours.Obtain phosphorus
Sour iron.
Embodiment 5-8
The ferric phosphate for respectively preparing embodiment 1-4 and comparative example 1 is with battery-level lithium carbonate powder according to 1:0.51 rubs
You are added the glucose for being equivalent to ferric phosphate weight fraction 15% and are equivalent to ferric phosphate, lithium carbonate and grape than mixing
2 times of deionized water of sugared total weight is ground, spray drying, and then in a nitrogen atmosphere, 700 DEG C of constant temperature calcining 8h are crushed,
Obtain LiFePO4 A1, A2, A3, A4, D1 of grey black.
Test case
(1) anode sizing agent is prepared：By the LiFePO4 of above-mentioned preparation and Super-P (Merk), PVDF (French A Ke codes
HSV900) according to 90:5:5 mass ratio mixing, specific method are：First using NMP as solvent, PVDF dissolvings are configured to 6 weights
The solution of % is measured, and under stiring respectively mixes carbon-coated LiFePO 4 for lithium ion batteries, Super-P with the solution of above-mentioned PVDF, is stirred later
It mixes to form uniform anode sizing agent；
(2) lithium ion battery is prepared：The anode sizing agent is uniformly coated on aluminium foil, then drying, roller at 100 DEG C
It presses, cut the anode that obtained size is 120mm × 160mm.Using graphite as cathode, above-mentioned positive and negative electrode is folded with polypropylene screen
At the battery core component of a square soft bag lithium ionic cell, then by LiPF6It is dissolved in EC/DMC=by the concentration of 1 mol/L
1:The in the mixed solvent of 1 (volume ratio) forms nonaqueous electrolytic solution, by the electrolyte in the amount injection battery case of 5g/Ah, to seal,
25Ah soft bag lithium ionic cells are made；
(3) high rate performance is tested：By above-mentioned made soft bag lithium ionic cell, carried out under the test condition of 25 DEG C of constant temperature times
Rate is tested, and 1. the electric current of 0.5C charges to 4.3V, shelves 10 minutes, then records its electric discharge to 2.5V with the current discharge of 0.5C
Capacity C 1.2. 0.5C charges, blanking voltage 4.3V, shelve 10 minutes, then with 5C current discharges, blanking voltage 2.5V, record
Its discharge capacity C5.3. calculating C5/C1*100%, the discharge capacity ratio of as 5C.10C discharge capacity ratio test methods and
Calculation formula is similar with 5C, only need to discharge current be adjusted to 10C；
(4) low temperature performance is tested：By above-mentioned made soft bag lithium ionic cell, carried out under the test condition of 0.5C low
Temperature test, 1. 25 DEG C of constant temperature, the electric current of 0.5C charge to 4.3V, shelve 10 minutes, then with the current discharge of 0.5C to 2.5V, remember
Record its discharge capacity C1.2. 25 DEG C of constant temperature 0.5C chargings, blanking voltage 4.3V.3. -10 DEG C are shelved 120 minutes, then with 0.5C
Current discharge, blanking voltage 2.5V record its discharge capacity C-10.3. calculating (C-10)/C1*100%, as -10 DEG C put
Capacitance ratio.- 20 DEG C of discharge capacity ratio test methods and calculation formula are similar with -10 DEG C, only need to by step shelving 3.
Temperature and discharge temp are adjusted to -20 DEG C.
Table 1 is the multiplying power discharging and low temperature performance data of A1, A2, A3, A4, D1：
Table 1
The LiFePO4 that the cellular ferric phosphate prepared by the method for the present invention obtains is can be seen that by the result of table 1
Positive electrode as battery has preferable high rate performance and cryogenic property.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of cellular ferric phosphate, which is characterized in that the preparation method includes：Organic porous material will be contained
Lotion, the solution containing molysite and the mixing of the solution containing phosphate radical, obtained mixed emulsion contacts with oxidant, will contact
Slurry is obtained after product pressure filtration washing afterwards, ageing is contacted with phosphoric acid after the pulp dilution, to the solids obtained after ageing
Material carries out high temperature sintering.
2. preparation method according to claim 1, wherein the organic porous material is macropore organic porous material, is situated between
At least one of hole organic porous material and micropore organic porous material；
Preferably, the aperture of the organic porous material is 10-150nm, preferably 20-110nm, further preferably 30-
80nm。
3. preparation method according to claim 1 or 2, wherein described in the lotion containing organic porous material
The content of organic porous material is 8-30 weight %；
Preferably, also contain surfactant in the lotion containing organic porous material.
4. preparation method according to claim 1, wherein in the solution containing molysite, the concentration of the molysite
For 0.6-2mol/L, preferably 0.8-1.5mol/L；
Preferably, the molysite is soluble ferrite；
It is further preferred that the molysite is ferrous sulfate and/or frerrous chloride.
5. preparation method according to claim 1, wherein in the solution containing phosphate radical, the concentration of phosphate radical
For 0.6-2mol/L, preferably 0.8-1.3mol/L；
Preferably, the phosphate radical is carried by least one of phosphoric acid, ammonium phosphate salt, ammonium hydrogen phosphate, sodium phosphate and dibastic sodium phosphate
For；
Preferably, the dosage of the iron ion in the solution containing molysite and the phosphate radical in the solution containing phosphate radical
Molar ratio be 0.98-1.03：1.
6. preparation method according to claim 1, wherein the dosage of the organic porous material is the mixed emulsion
1-17 weight %, preferably 2-10 weight %.
7. preparation method according to claim 1, wherein the oxidant is hydrogen peroxide and/or hypochlorous acid；
Preferably, the preparation method further includes：Before the product after contacting carries out pressure filtration washing, adjusted with lye described in
The pH of product after contact is 1.6-3.2, preferably 2-2.8.
8. preparation method according to claim 1, wherein the temperature of the high temperature sintering is 400-680 DEG C, preferably
450-640℃；
Preferably, the preparation method further includes：After the ageing and before the high temperature sintering, to being obtained after the ageing
Material carry out washing and press filtration and slough Free water.
9. the cellular ferric phosphate being prepared by the preparation method described in any one of claim 1-8.
10. a kind of LiFePO4, which is characterized in that the LiFePO4 is made of the raw material containing ferric phosphate, the ferric phosphate
For the cellular ferric phosphate described in claim 9.
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| CN112713272A (en) * | 2020-12-18 | 2021-04-27 | 浙江金鹰瓦力新能源科技有限公司 | Preparation method of modified lithium battery positive electrode material |
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| CN114583159A (en) * | 2022-02-24 | 2022-06-03 | 合肥国轩高科动力能源有限公司 | Low-temperature lithium iron phosphate cathode material, and preparation method and application thereof |
| CN115448275A (en) * | 2022-08-03 | 2022-12-09 | 宜都兴发化工有限公司 | Method for preparing mesoporous iron phosphate by inducing block copolymer |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112713272A (en) * | 2020-12-18 | 2021-04-27 | 浙江金鹰瓦力新能源科技有限公司 | Preparation method of modified lithium battery positive electrode 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 |
| CN114583159A (en) * | 2022-02-24 | 2022-06-03 | 合肥国轩高科动力能源有限公司 | Low-temperature lithium iron phosphate cathode material, and preparation method and application thereof |
| CN114583159B (en) * | 2022-02-24 | 2023-08-04 | 合肥国轩高科动力能源有限公司 | Low-temperature lithium iron phosphate positive electrode material, preparation method and application thereof |
| CN115448275A (en) * | 2022-08-03 | 2022-12-09 | 宜都兴发化工有限公司 | Method for preparing mesoporous iron phosphate by inducing block copolymer |
| CN115448275B (en) * | 2022-08-03 | 2023-11-24 | 宜都兴发化工有限公司 | Method for preparing mesoporous ferric phosphate by induction of block copolymer |
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