CN102464309A - Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide - Google Patents
Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide Download PDFInfo
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- CN102464309A CN102464309A CN2010105530792A CN201010553079A CN102464309A CN 102464309 A CN102464309 A CN 102464309A CN 2010105530792 A CN2010105530792 A CN 2010105530792A CN 201010553079 A CN201010553079 A CN 201010553079A CN 102464309 A CN102464309 A CN 102464309A
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- phosphoric acid
- lithium
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- iron
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 164
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 82
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 15
- 150000003839 salts Chemical class 0.000 title abstract description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 28
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 claims description 27
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 20
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 20
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 238000011160 research Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000006210 lotion Substances 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 10
- 150000002978 peroxides Chemical class 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 8
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000005955 Ferric phosphate Substances 0.000 claims description 6
- 229940032958 ferric phosphate Drugs 0.000 claims description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002120 nanofilm Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 2
- 230000005484 gravity Effects 0.000 abstract 1
- 239000013081 microcrystal Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- 239000000463 material Substances 0.000 description 15
- 239000011572 manganese Substances 0.000 description 10
- 239000002699 waste material Substances 0.000 description 9
- -1 Lithium Hydroxide MonoHydrate phosphate dihydrate iron Chemical compound 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 229910010710 LiFePO Inorganic materials 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 238000005649 metathesis reaction Methods 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910001447 ferric ion Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 3
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 229910001037 White iron Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- ALWLKPJUHXAWMB-UHFFFAOYSA-M [Fe+].C(C)C(COP(=O)(OCC(CCCC)CC)[O-])CCCC Chemical compound [Fe+].C(C)C(COP(=O)(OCC(CCCC)CC)[O-])CCCC ALWLKPJUHXAWMB-UHFFFAOYSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide, which comprises the following steps that: phosphoric acid solution takes reaction with the scrap iron, when the pH value of reaction liquid A is greater than or equal to 1.5, or the specific gravity is 1.28 to 1.31, the reaction liquid A is collected and is transferred into an oxidation tank, the pH value is regulated to a value higher than 2, hydrogen peroxide is added under the stirring until white powder B is generated in the solution, and the pH value in the solution is maintained to be greater than 2 in the hydrogen peroxide adding process; the solution is slowly stirred and heated for crystallization when no new precipitates are generated in the solution, the crystals are separated and washed, and solid powder B is obtained; the solid powder B is uniformly mixed with lithium hydroxide solution containing pyrolysis carbon sources to obtain suspension C; the suspension C is dried to obtain precursors D; and the precursors D are subjected to two-stage roasting in reducing atmosphere, the temperature is 450 to 500 DEG C in the first stage, the temperature is 650 to 750 DEG C in the second stage, and the battery positive electrode materials are prepared. The submicron particle powder lithium iron phosphate complex salt with the nanometer microcrystal particles uniformly coated and bridged by the pyrolysis carbon is obtained, the lithium iron phosphate complex salt has high tap density and is uniform, and good conduction performance and electrochemical performance are realized.
Description
Technical field
The present invention relates to a kind ofly prepare the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium, belong to the new energy materials field with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate.
Background technology
Development new forms of energy, low-carbon economy and energy-saving and emission-reduction have become the task of top priority of countries in the world development; Electromobile and new-energy automobile are the new milestones of 21st century automobile industry development; To alleviating global energy crisis, strengthen environmental protection has special and far reaching significance.
Lithium-ion secondary cell is the new generation of green energy, and it mainly is made up of positive pole, negative pole, ionogen three big materials, has advantages such as high-energy-density, high cycle performance, low self-discharge rate, memory-less effect, operating temperature range be wide.At present in numerous areas widespread uses such as mobile telephone, laptop computer, pick up camera, power tools, and marching to electric automobiles fast.
At present, the maximum lithium ion secondary battery anode material of research is LiCoO
2, LiNiO
2, LiMn
2O
4LiCoO
2Be positive electrode material than large-scale commercial morning, the research comparative maturity, high comprehensive performance, but cost an arm and a leg, capacity is lower.LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, there are comparatively serious safety-problems in the consistence of material property and poor reproducibility.Spinel LiMn
2O
4Cost is low, and security is good, but capacity is low, and the Tahn-Teller effect takes place when deep discharge, influences the stability of material structure, and the high temperature cyclic performance of material is poor.Stratiform LiMnO
2Specific storage is bigger, but it belongs to the thermodynamics metastable state, and there is the Jahn-Teller effect in structural instability and cycle performance is relatively poor.Stratiform LiNi
xCo
yMn
1-x-yO
2Series material (abbreviation ternary material) is like LiNi
1/3Co
1/3Mn
1/3O
2The advantage that has had both the three preferably; Having remedied deficiency separately, had that height ratio capacity, cost are lower, characteristics such as stable cycle performance, safety performance are better, is the strong rival of anode material for lithium-ion batteries of future generation; But still have industrial synthetic process comparatively complicated; Presoma prepares poor repeatability, and the fillibility of powder is undesirable, and expensive Ni, Co element ratio are than problems such as height.
Goodenough working groups in 1997 find the LiFePO of quadrature olivine structural
4Redox potential be 3.4V, cycle performance is better, theoretical capacity reaches 170mAh/g, causes the very big interest of numerous scientific workers and many companies.The LiFePO of olivine structural
4Stable operating voltage, platform identity is good, capacity is higher, Stability Analysis of Structures, high-temperature behavior and good cycle, safety non-toxic, with low cost.See from present Status of development, and consider LiFePO from long-range viewpoint such as cost performance, resource and environment
4It is up-and-coming lithium ion secondary battery anode material of new generation.But see that from power truck situation on probation in extensive range the LiFePO 4 existing problems of producing at present are: the still difficult satisfied 10 years universal demands that use of the homogeneity of material, tap density is little, and specific storage is lower etc.
Summary of the invention
The novel method that the purpose of this invention is to provide the ferrous salt of phosphoric acid positive electrode material of lithium that a kind of crystal grain for preparing with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate is little, the life-span long, tap density is big, specific storage is higher.
Provided by the present inventionly prepare the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium, comprise the steps: with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate
Phosphoric acid solution and iron filings reaction; When the pH of reaction solution value >=1.5 or proportion 1.28～1.31; Collection contains the reaction soln A of ferrous dihydrogen phosphate and transfers in the oxidation tank; Regulate pH value greater than 2, under agitation add ydrogen peroxide 50 ferrous dihydrogen phosphate is oxidized to phosphate dihydrate iron and by product phosphoric acid, add in the ydrogen peroxide 50 process make up water with maintenance pH value of solution value greater than 2;
When no white precipitate produces in the solution after adding ydrogen peroxide 50, slowly stir and heating crystallization,, obtain white phosphate dihydrate iron pressed powder B and the mother liquor and the washing lotion G that contain by product phosphoric acid Crystallization Separation and washing;
Pressed powder B obtains suspension liquid C with the lithium hydroxide solution uniform mixing that contains the pyrolysis carbon source;
Suspension liquid C spraying drying obtains the high ferric phosphate crystallite by the precursor D of sucrose and Lithium Hydroxide MonoHydrate molecular film parcel;
Said precursor D carries out two-stage roasting under reducing atmosphere, first section is 450～500 ℃, and second section is 650～750 ℃, makes the ferrous salt of phosphoric acid of lithium and is coated the also anode material for lithium-ion batteries of bridging with nano microcrystalline by RESEARCH OF PYROCARBON.
Of the present inventionly prepare the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate, wherein said phosphoric acid solution is 2.8～3.1 mol.
Of the present inventionly prepare the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate, the temperature of wherein said phosphoric acid solution and the reaction of said iron filings remains on 50～70 ℃.
Of the present inventionly prepare the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate, the mol ratio of wherein said white phosphate dihydrate iron pressed powder B, said Lithium Hydroxide MonoHydrate, said RESEARCH OF PYROCARBON is (1.00): (1.00～1.05): (0.70～1.16).
Of the present inventionly prepare the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate, wherein said reducing atmosphere is under the mixed gas condition of volume percent 5～15% hydrogen and volume percent 95～85% nitrogen or argon gas or under the mixed gas condition of 100 parts of decomposed ammonias and 400～67 parts of nitrogen or argon gas.
Of the present inventionly prepare the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate, wherein said pyrolysis carbon source be selected from sucrose, glucose, Hydrocerol A, starch and the Z 150PH any or appoint several kinds.
Of the present inventionly prepare the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate, wherein said hydrogen peroxide concentration is 27.5%.
Of the present inventionly prepare the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate, wherein said mother liquor that contains by product phosphoric acid and washing lotion G are used to join phosphoric acid solution and recycle.
The present invention prepares the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium and produces high ferric phosphate cheaply with iron filings phosphoric acid ydrogen peroxide 50 direct replacement oxidation with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate; Then the advanced row of Lithium Hydroxide MonoHydrate phosphate dihydrate iron pyrolysis carbon source material by wet type mixing is made the ferrous salt of phosphoric acid of lithium with the pyrocarbon reduction again; Obtain evenly being coated the also ferrous salt of phosphoric acid of submicron particle powder lithium of bridging by RESEARCH OF PYROCARBON with the nano microcrystalline particle; The ferrous salt of phosphoric acid tap density of this lithium is higher and more even, has good conductivity and chemical property.
Description of drawings
Fig. 1 is the 2FePO of embodiment 1 preparation
42H
2The X-ray diffracting spectrum of O.
Fig. 2 is the LiFePO of embodiment 1 preparation
4X-ray diffracting spectrum.
Fig. 3 is the LiFePO of preparation
4Do the 18650 type 1200mAh cylindrical lithium ion battery 1C charging of positive electrode active material preparation, difference 0.2C, 1C, 5C discharge curve.
Fig. 4 is the prepared LiFePO of embodiment 1
4Do the 18650 type 1200mAh cylindrical lithium ion battery 1C charging of positive electrode active material preparation, 10C discharge cycles curve.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described further.
The first step: precipitate legal system phosphate dihydrate iron with solution oxide again with the ferrous phosphate dihydrogen salt solution of iron filings phosphoric acid solution system earlier.
Waste iron filing: battery industry is produced the waste iron filing of the hardware factory of cell device, porous scrap iron band, and the BDCK of material such as Baosteel or SPCC: impurities manganese high slightly (Mn≤0.3%) only wherein, but manganese is harmless useful alloying element.
Waste iron filing is filled retort from the top feeding mouth, and 3.1 mol phosphoric acid solutions add reactor drum and enable to soak full iron filings, and 3.1 mol phosphoric acid solutions are that commercially available 85% phosphoric acid and water are mixed and made into according to volume ratio at 1: 3.7; The chuck heating makes temperature of reactor remain on 50～60 ℃ following replacement(metathesis)reaction is comparatively fast carried out:
Fe+2H
3PO
4＝Fe(H
2PO
4)
2+H
2↑ (1)
When speed of response is slack-off, progressively be heated to 70 ℃ to promote reaction, the hydrogen that reaction produces is from the logical outdoor emptying of reactor head vapor pipe, and water of condensation flows back to retort in the pipe; When also not producing hydrogen basically for 70 ℃, think to react and accomplish; This moment test reaction liquid pH value=1.5, proportion=1.31 are all put into oxidation tank with the reaction solution of heat through filter screen; The phosphate dihydrogen salt solution A of iron is through chemical analysis: Fe1.3357mol/L, PO in the oxidation tank
43.2314mol/L; Add enough phosphoric acid solutions behind the additional iron filings of retort and carry out the next round replacement(metathesis)reaction.
Solution adds the white tertiary iron phosphate of the ferrous generation of biphosphate (phosphate dihydrate iron) the pressed powder precipitate B (add water in the oxidising process at any time and keep the pH value of solution value greater than 2) in the ydrogen peroxide 50 direct oxidation solution to its pH value=2.5 in the dilution oxidation tank under stirring energetically:
2Fe(H
2PO
4)
2+H
2O
2+2H
2O＝2FePO
4·2H
2O↓+2H
3PO
4......(2)
When proceeding to, oxidation thinks that deposition fully when not had ferrous ion (checking) in the solution with the Tripotassium iron hexacyanide; Change slow stirring and be heated to 80 ℃ of insulation crystallizations 10 hours; Phosphate dihydrate iron powder B is carried out spinning and washing with the mother liquor that contains by product phosphoric acid; When inspection in the washing lotion finishes during less than ferric ion (checking with yellow prussiate of potash), mother liquor and washing lotion are used to join dilute phosphoric acid and recycle, isolated phosphate dihydrate iron powder B do not dry direct entering next step;
Second step: the advanced row of Lithium Hydroxide MonoHydrate phosphate dihydrate iron pyrolysis carbon source material by wet type mixing is made the ferrous salt of phosphoric acid of lithium with the pyrocarbon reduction again:
The phosphate dihydrate iron powder B:Fe27.84% that chemical analysis dries, P15.611%; Iron phosphorus mol ratio=0.4985: 0.5040=0.9891: 1.0000; The aqueous solution of joining 1.02 moles of hydrogen Lithium Oxide 98mins and 20 gram sucrose by every mole of phosphate dihydrate iron (in phosphorus); And the phosphate dihydrate iron powder that under stirring energetically, will wet all adds; Stir suspension liquid C, suspension liquid C spraying drying is got the high ferric phosphate crystallite by the precursor D of sucrose and Lithium Hydroxide MonoHydrate molecular film parcel, precursor D (100 parts by volume decomposed ammonias and 100 parts by volume nitrogen) 500 ℃ of roastings 6 hours under weakly reducing atmosphere; 700 ℃ of roastings 12 hours, 700 ℃ of following roasting net reactions can be abbreviated as:
2LiOH+2FePO
4·2H
2O+C＝2LiFePO
4+CO+5H
2O......(3)
While or the decomposition of successively carrying out, reduction, combination reaction can make the ferrous salt of phosphoric acid of lithium and coated the also submicron powder anode material for lithium-ion batteries of bridging with nano microcrystalline by RESEARCH OF PYROCARBON.
Fig. 1 is the X-ray diffracting spectrum of made iron di(2-ethylhexyl)phosphate water salt, and Fig. 2 is the ferrous salt of phosphoric acid positive electrode material of a made lithium X-ray diffracting spectrum, and Fig. 3 and Fig. 4 are the ferrous salt of phosphoric acid positive electrode material of made lithium chemical property figure.
The first step: precipitate legal system phosphate dihydrate iron with solution oxide again with the ferrous aqueous phosphate solution of iron filings phosphoric acid solution system earlier;
Waste iron filing: battery industry is produced the waste iron filing of the hardware factory of cell device, porous scrap iron band, and the BDCK of material such as Baosteel or SPCC: impurities manganese high slightly (Mn≤0.3%) only wherein, but manganese is harmless useful alloying element.
Waste iron filing is filled retort from the top feeding mouth, and 2.7 mol phosphoric acid solutions add reactor drum and enable to soak full iron filings, and 2.7 mol phosphoric acid solutions are that commercially available 85% phosphoric acid and water are mixed and made into according to volume ratio at 1: 4.4; The chuck heating makes temperature of reactor remain on 50～60 ℃ following replacement(metathesis)reaction is comparatively fast carried out:
Fe+2H
3PO
4＝Fe(H
2PO
4)
2+H
2↑ (1)
When speed of response is slack-off, progressively be heated to 70 ℃ to promote reaction, the hydrogen that reaction produces is from the logical outdoor emptying of reactor head vapor pipe, and water of condensation flows back to retort in the pipe; When also not producing hydrogen basically for 70 ℃, think to react and accomplish; This moment test reaction liquid pH value=3, proportion=1.28 are all put into oxidation tank with the reaction solution of heat through filter screen; The phosphate dihydrogen salt solution A of iron is through chemical analysis in the oxidation tank: Fe 1.2957mol/L, PO
43.1822mol/L; Add enough phosphoric acid solutions behind the additional iron filings of retort and carry out the next round replacement(metathesis)reaction.
Phosphoric acid salt (phosphate dihydrate iron) the pressed powder precipitate B (add water in the oxidising process at any time and keep the pH value of solution value) that under stirring energetically, adds the white iron of the ferrous generation of biphosphate in the ydrogen peroxide 50 direct oxidation solution greater than 2:
2Fe(H
2PO
4)
2+H
2O
2+2H
2O＝2FePO
4·2H
2O↓+2H
3PO
4......(2)
When proceeding to, oxidation thinks that deposition fully when not had ferrous ion (checking) in the solution with the Tripotassium iron hexacyanide; Change slow stirring and be heated to 80 ℃ of insulation crystallizations 6 hours; Phosphate dihydrate iron powder B is carried out spinning and washing with the mother liquor that contains by product phosphoric acid; When inspection in the washing lotion finishes during less than ferric ion (checking with yellow prussiate of potash), mother liquor and washing lotion are used to join dilute phosphoric acid and recycle, isolated phosphate dihydrate iron powder B do not dry direct entering next step;
Second step: the advanced row of Lithium Hydroxide MonoHydrate phosphate dihydrate iron pyrolysis carbon source material by wet type mixing is made the ferrous salt of phosphoric acid of lithium with the pyrocarbon reduction again,
The chemical analysis phosphate dihydrate iron powder B:Fe28.1% that wets; P15.82%, iron phosphorus mol ratio=0.5032: 0.5108=0.9852: 1.0000, join the aqueous solution that 1.00 moles of hydrogen Lithium Oxide 98mins and 23.5 restrain sucrose by every mole of phosphate dihydrate iron (in phosphorus); And the phosphate dihydrate iron powder that under stirring energetically, will wet all adds; Stir suspension liquid C, suspension liquid C spraying drying is got the high ferric phosphate crystallite by the precursor D of sucrose and Lithium Hydroxide MonoHydrate molecular film parcel, precursor D (5 parts by volume hydrogen and 95 parts by volume argon gas) 450 ℃ of roastings 12 hours under weakly reducing atmosphere; 750 ℃ of roastings 8 hours, 750 ℃ of following roasting net reactions can be abbreviated as:
2LiOH+2FePO
4·2H
2O+C＝2LiFePO
4+CO+5H
2O......(3)
While or the decomposition of successively carrying out, reduction, combination reaction can make the ferrous salt of phosphoric acid of lithium with the anode material for lithium-ion batteries in the electronic conduction network of nano microcrystalline embedding RESEARCH OF PYROCARBON formation.
Embodiment 3
The first step: precipitate legal system phosphate dihydrate iron with solution oxide again with the ferrous aqueous phosphate solution of iron filings phosphoric acid solution system earlier;
Waste iron filing: battery industry is produced the waste iron filing of the hardware factory of cell device, porous scrap iron band, and the BDCK of material such as Baosteel or SPCC: impurities manganese high slightly (Mn≤0.3%) only wherein, but manganese is harmless useful alloying element.
Waste iron filing is filled retort from the top feeding mouth, and 2.9 mol phosphoric acid solutions add reactor drum and enable to soak full iron filings, and 2.9 mol phosphoric acid solutions are that commercially available 85% phosphoric acid and water are mixed and made into according to volume ratio at 1: 4.0; The chuck heating makes temperature of reactor remain on 50～60 ℃ following replacement(metathesis)reaction is comparatively fast carried out:
Fe+2H
3PO
4＝Fe(H
2PO
4)
2+H
2↑ (1)
When speed of response is slack-off, progressively be heated to 70 ℃ to promote reaction, the hydrogen that reaction produces is from the logical outdoor emptying of reactor head vapor pipe, and water of condensation flows back to retort in the pipe; When also not producing hydrogen basically for 70 ℃, think to react and accomplish; This moment test reaction liquid pH value=2, proportion=1.30 are all put into oxidation tank with the reaction solution of heat through filter screen; The phosphate dihydrogen salt solution A of iron is through chemical analysis in the oxidation tank: Fe 1.3208mol/L, PO
43.1905mol/L; Fill up phosphoric acid solution behind the additional iron filings of retort and carry out the next round replacement(metathesis)reaction.
Phosphoric acid salt (phosphate dihydrate iron) the pressed powder precipitate B (add water in the oxidising process at any time and keep the pH value of solution value) that under stirring energetically, adds the white iron of the ferrous generation of biphosphate in the ydrogen peroxide 50 direct oxidation solution greater than 2:
2Fe(H
2PO
4)
2+H
2O
2+2H
2O＝2FePO
4·2H
2O↓+2H
3PO
4......(2)
Oxidising process keeps the pH value of solution value greater than 2 to be because there is by product phosphoric acid to generate [seeing reaction formula (2)] in the oxidising process, and phosphoric acid acidity Fe (H when big
2PO
4)
2The ferrous ion oxidation maybe be incomplete, and ferric iron can be with Fe (H
2PO
4)
3State exists makes FePO in the solution
42H
2The O deposition not exclusively; When proceeding to, oxidation thinks that deposition fully when not had ferrous ion (checking) in the solution with the Tripotassium iron hexacyanide; Change slow stirring and be heated to and be incubated crystallization 12 hours about 70～80 ℃; Phosphate dihydrate iron powder B is carried out spinning and washing with the mother liquor that contains by product phosphoric acid; When inspection in the washing lotion finishes during less than ferric ion (checking with yellow prussiate of potash), mother liquor and washing lotion are used to join dilute phosphoric acid and recycle, isolated phosphate dihydrate iron powder B do not dry direct entering next step;
Second step: the advanced row of Lithium Hydroxide MonoHydrate phosphate dihydrate iron pyrolysis carbon source material by wet type mixing is made the ferrous salt of phosphoric acid of lithium with the pyrocarbon reduction again,
The chemical analysis phosphate dihydrate iron powder B:Fe27.43% that wets; P15.35%, iron phosphorus mol ratio=0.4912: 0.4956=0.9912: 1.0000, join the aqueous solution that 1.04 moles of hydrogen Lithium Oxide 98mins and 32.8 restrain sucrose by every mole of phosphate dihydrate iron (in phosphorus); And the phosphate dihydrate iron powder that under stirring energetically, will wet all adds; Stir suspension liquid C, suspension liquid C spraying drying is got the high ferric phosphate crystallite by the precursor D of sucrose and Lithium Hydroxide MonoHydrate molecular film parcel, precursor D (15 parts by volume hydrogen and 85 parts by volume nitrogen) 500 ℃ of roastings 4 hours under weakly reducing atmosphere; 680 ℃ of roastings 20 hours, 680 ℃ of following roasting net reactions can be abbreviated as:
2LiOH+2FePO
4·2H
2O+C＝2LiFePO
4+CO+5H
2O......(3)
While or the decomposition of successively carrying out, reduction, combination reaction can make the ferrous salt of phosphoric acid of lithium with the anode material for lithium-ion batteries in the electronic conduction network of nano microcrystalline embedding RESEARCH OF PYROCARBON formation.
Above embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (9)
1. prepare the novel method of the ferrous salt of phosphoric acid positive electrode material of lithium with iron filings, phosphoric acid, Lithium Hydroxide MonoHydrate, comprise the steps:
Phosphoric acid solution and iron filings reaction; When the pH of reaction solution value >=1.5 or proportion 1.28～1.31; Collection contains the reaction soln A of ferrous dihydrogen phosphate and transfers in the oxidation tank; Regulate pH value greater than 2, under agitation add ydrogen peroxide 50 ferrous dihydrogen phosphate is oxidized to phosphate dihydrate iron and by product phosphoric acid, add in the ydrogen peroxide 50 process make up water with maintenance pH value of solution value greater than 2;
When no white precipitate produces in the solution after adding ydrogen peroxide 50, slowly stir and heating crystallization,, obtain white phosphate dihydrate iron pressed powder B and the mother liquor and the washing lotion G that contain by product phosphoric acid Crystallization Separation and washing;
Pressed powder B obtains suspension liquid C with the lithium hydroxide solution uniform mixing that contains the pyrolysis carbon source;
Suspension liquid C spraying drying obtains the high ferric phosphate crystallite by the precursor D of sucrose and Lithium Hydroxide MonoHydrate molecular film parcel;
Said precursor D carries out two-stage roasting under reducing atmosphere, first section is 450～500 ℃, and second section is 650～750 ℃, makes the ferrous salt of phosphoric acid of lithium and is coated the also anode material for lithium-ion batteries of bridging with nano microcrystalline by RESEARCH OF PYROCARBON.
2. novel method according to claim 1 is characterized in that: said phosphoric acid solution is 2.8～3.1 mol.
3. novel method according to claim 1 is characterized in that: the temperature of said phosphoric acid solution and the reaction of said iron filings remains on 50～70 ℃.
4. novel method according to claim 1 is characterized in that: the mol ratio of said white phosphate dihydrate iron pressed powder B, said Lithium Hydroxide MonoHydrate, said RESEARCH OF PYROCARBON is (1.00): (1.00～1.05): (0.70～116).
5. novel method according to claim 1 is characterized in that: said reducing atmosphere is under the mixed gas condition of volume percent 5～15% hydrogen and volume percent 95～85% nitrogen or argon gas or under the mixed gas condition of 100 parts of decomposed ammonias and 400～67 parts of nitrogen or argon gas.
6. novel method according to claim 1 is characterized in that: said pyrolysis carbon source be selected from sucrose, glucose, Hydrocerol A, starch and the Z 150PH any or appoint several kinds.
7. novel method according to claim 1 is characterized in that: said hydrogen peroxide concentration is 27.5%.
8. novel method according to claim 1, its characteristic also is: said mother liquor that contains by product phosphoric acid and washing lotion G are used to join phosphoric acid solution and recycle.
9. the ferrous salt of phosphoric acid nano microcrystalline of the lithium particle of arbitrary described novel method preparation is evenly coated the also ferrous salt of phosphoric acid positive electrode material of lithium of the submicron particle powder of bridging by RESEARCH OF PYROCARBON in the claim 1 to 8.
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| CN104817059A (en) * | 2015-04-29 | 2015-08-05 | 江西东华科技园有限责任公司 | Method for preparing battery-grade iron phosphate from reaction between iron powder and phosphoric acid |
| CN105480960A (en) * | 2015-12-29 | 2016-04-13 | 河北斯霖百特新能源科技有限公司 | Iron phosphate preparation method |
| CN106517128A (en) * | 2016-11-08 | 2017-03-22 | 河南省净寰新能源科技有限公司 | Low-cost cell-grade ferric phosphate micro powder preparation method |
| CN107032316A (en) * | 2017-06-12 | 2017-08-11 | 百川化工(如皋)有限公司 | A kind of preparation method of ferric phosphate |
| CN107522187A (en) * | 2017-07-18 | 2017-12-29 | 江西悦安超细金属有限公司 | A kind of ferric phosphate and preparation method thereof |
| CN107611427A (en) * | 2016-07-12 | 2018-01-19 | 南通亨利锂电新材料有限公司 | A kind of microstructure metal phosphate and preparation method thereof |
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| CN115818603A (en) * | 2022-12-02 | 2023-03-21 | 湖南顺华锂业有限公司 | Method for preparing battery-grade iron phosphate from residues generated after lithium extraction by oxidizing lithium iron phosphate positive electrode powder containing copper, aluminum and graphite |
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| CN104817059A (en) * | 2015-04-29 | 2015-08-05 | 江西东华科技园有限责任公司 | Method for preparing battery-grade iron phosphate from reaction between iron powder and phosphoric acid |
| CN105480960A (en) * | 2015-12-29 | 2016-04-13 | 河北斯霖百特新能源科技有限公司 | Iron phosphate preparation method |
| CN107611427A (en) * | 2016-07-12 | 2018-01-19 | 南通亨利锂电新材料有限公司 | A kind of microstructure metal phosphate and preparation method thereof |
| CN106517128A (en) * | 2016-11-08 | 2017-03-22 | 河南省净寰新能源科技有限公司 | Low-cost cell-grade ferric phosphate micro powder preparation method |
| CN107032316A (en) * | 2017-06-12 | 2017-08-11 | 百川化工(如皋)有限公司 | A kind of preparation method of ferric phosphate |
| CN107522187A (en) * | 2017-07-18 | 2017-12-29 | 江西悦安超细金属有限公司 | A kind of ferric phosphate and preparation method thereof |
| CN107863531A (en) * | 2017-11-03 | 2018-03-30 | 山东科技大学 | A kind of method that anode material for lithium-ion batteries is prepared using siderite |
| CN115818603A (en) * | 2022-12-02 | 2023-03-21 | 湖南顺华锂业有限公司 | Method for preparing battery-grade iron phosphate from residues generated after lithium extraction by oxidizing lithium iron phosphate positive electrode powder containing copper, aluminum and graphite |
| CN115818603B (en) * | 2022-12-02 | 2024-03-12 | 湖南顺华锂业有限公司 | Method for preparing battery grade ferric phosphate from lithium iron phosphate anode powder containing copper, aluminum and graphite through oxidizing and extracting lithium from residue |
| CN116462173A (en) * | 2023-06-01 | 2023-07-21 | 云南云天化股份有限公司 | Method for preparing ferric phosphate by iron method |
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