CN102464309B - 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
- Publication number
- CN102464309B CN102464309B CN201010553079.2A CN201010553079A CN102464309B CN 102464309 B CN102464309 B CN 102464309B CN 201010553079 A CN201010553079 A CN 201010553079A CN 102464309 B CN102464309 B CN 102464309B
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- lithium
- solution
- iron
- lithium hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 160
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 80
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 75
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000003839 salts Chemical class 0.000 title abstract description 9
- 239000007774 positive electrode material Substances 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
- 239000000843 powder Substances 0.000 claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002243 precursor 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
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 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
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-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
- 239000007788 liquid Substances 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 239000006210 lotion Substances 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- 238000011160 research Methods 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 8
- 239000005955 Ferric phosphate Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229940032958 ferric phosphate Drugs 0.000 claims description 7
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 7
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002120 nanofilm Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 239000004372 Polyvinyl alcohol Substances 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
- 239000008103 glucose Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 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
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 2
- 239000000725 suspension 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 32
- 239000000463 material Substances 0.000 description 15
- -1 lithium hydroxide phosphate dihydrate iron Chemical compound 0.000 description 11
- 239000011572 manganese Substances 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- 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
- 238000006073 displacement reaction Methods 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229940116007 ferrous phosphate Drugs 0.000 description 5
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 208000015924 Lithiasis Diseases 0.000 description 3
- 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910001447 ferric ion Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000009413 insulation Methods 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
- 239000000276 potassium ferrocyanide Substances 0.000 description 3
- 230000036632 reaction speed Effects 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
- 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
- 238000007600 charging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 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
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JLLMDXDAVKMMEG-UHFFFAOYSA-N hydrogen peroxide phosphoric acid Chemical compound OO.OP(O)(O)=O JLLMDXDAVKMMEG-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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 of new method of preparing the ferrous salt of phosphoric acid positive electrode of lithium with iron filings, phosphoric acid, lithium hydroxide, belong to new energy materials field.
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; electric automobile 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 rechargeable battery is the new generation of green energy, and it is mainly made up of positive pole, negative pole, the large material of electrolyte three, has the 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 extensive uses such as mobile phone, laptop computer, video camera, electric tools, and marching to electric automobiles fast.
At present, the lithium ion secondary battery anode material of most study is LiCoO
2, LiNiO
2, LiMn
2o
4.LiCoO
2the positive electrode of large-scale commercial early, research comparative maturity, high comprehensive performance, but expensive, capacity is lower.LiNiO
2cost is lower, and capacity is higher, but preparation difficulty,, there is comparatively serious safety problem in the consistency of material property and poor reproducibility.Spinelle LiMn
2o
4cost is low, and fail safe is good, but capacity is low, and Tahn-Teller effect occurs in the time of deep discharge, affects the stability of material structure, and the high temperature cyclic performance of material is poor.Stratiform LiMnO
2specific capacity is larger, but it belongs to thermodynamics metastable state, and structural instability, exists Jahn-Teller effect and cycle performance is poor.Stratiform LiNi
xco
ymn
1-x-yo
2series material (abbreviation ternary material) is as LiNi
1/3co
1/3mn
1/3o
2have both preferably three's advantage, make up deficiency separately, have that height ratio capacity, cost are lower, the feature such as stable cycle performance, security performance are better, the strong competitor of anode material for lithium-ion batteries of future generation, but still have industrial synthetic process comparatively complicated, the problems such as presoma is prepared poor repeatability, and the fillibility of powder is undesirable, and expensive Ni, Co element ratio is higher.
Goodenough working groups in 1997 find the LiFePO of orthogonal olivine structural
4oxidation-reduction 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.From current state of development, and consider LiFePO from the long-term perspective such as cost performance, resources and environment
4it is up-and-coming lithium ion secondary battery anode material of new generation.But from electric motor car situation on probation in extensive range, the LiFePO 4 existing problems of producing are at present: the uniformity of material is the difficult satisfied generally requirement in 10 years that uses still, and tap density is little, and specific capacity is lower etc.
Summary of the invention
The object of this invention is to provide the new method of the ferrous salt of phosphoric acid positive electrode of lithium that a kind of crystal grain of preparing with iron filings, phosphoric acid, lithium hydroxide is little, the life-span long, tap density is large, specific capacity is higher.
The new method of preparing the ferrous salt of phosphoric acid positive electrode of lithium with iron filings, phosphoric acid, lithium hydroxide provided by the present invention, comprises the steps:
Phosphoric acid solution reacts with iron filings, in the time of pH value >=1.5 of reactant liquor or proportion 1.28～1.31, collect and contain the reaction solution A of ferrous dihydric phosphate and transfer in oxidation tank, regulate pH value to be greater than 2, under agitation add hydrogen peroxide ferrous dihydric phosphate is oxidized to phosphate dihydrate iron and accessory substance phosphoric acid, add supplementing water in hydrogen peroxide process and be greater than 2 with maintenance pH;
When adding while producing without white precipitate in solution after hydrogen peroxide, slowly stir and heating crystallization, by Crystallization Separation washing, obtain white phosphate dihydrate iron pressed powder B and mother liquor and washing lotion G containing accessory substance phosphoric acid;
Pressed powder B is evenly mixed to get suspension-turbid liquid C with the lithium hydroxide solution containing pyrolysis carbon source;
The dry high ferric phosphate crystallite that obtains of suspension-turbid liquid C spraying is by the precursor D of sucrose and lithium hydroxide molecular film parcel;
Described precursor D carries out two-stage roasting under reducing atmosphere, and first paragraph is 450～500 DEG C, and second segment is 650～750 DEG C, 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.
The new method of preparing the ferrous salt of phosphoric acid positive electrode of lithium with iron filings, phosphoric acid, lithium hydroxide of the present invention, wherein said phosphoric acid solution is 2.8～3.1 mol/L.
The new method of preparing the ferrous salt of phosphoric acid positive electrode of lithium with iron filings, phosphoric acid, lithium hydroxide of the present invention, the temperature that wherein said phosphoric acid solution reacts with described iron filings remains on 50～70 DEG C.
The new method of preparing the ferrous salt of phosphoric acid positive electrode of lithium with iron filings, phosphoric acid, lithium hydroxide of the present invention, the mol ratio of wherein said white phosphate dihydrate iron pressed powder B, described lithium hydroxide, described RESEARCH OF PYROCARBON is (1.00): (1.00～1.05): (0.70～1.16).
The new method of preparing the ferrous salt of phosphoric acid positive electrode of lithium with iron filings, phosphoric acid, lithium hydroxide of the present invention, wherein said reducing atmosphere is under the mist condition of percent by volume 5～15% hydrogen and percent by volume 95～85% nitrogen or argon gas or under the mist condition of 100 parts of decomposed ammonias and 400～67 parts of nitrogen or argon gas.
The new method of preparing the ferrous salt of phosphoric acid positive electrode of lithium with iron filings, phosphoric acid, lithium hydroxide of the present invention, wherein said pyrolysis carbon source be selected from sucrose, glucose, citric acid, starch and polyvinyl alcohol any or appoint several.
The new method of preparing the ferrous salt of phosphoric acid positive electrode of lithium with iron filings, phosphoric acid, lithium hydroxide of the present invention, wherein said hydrogen peroxide concentration is 27.5%.
The new method of preparing the ferrous salt of phosphoric acid positive electrode of lithium with iron filings, phosphoric acid, lithium hydroxide of the present invention, the wherein said mother liquor containing accessory substance phosphoric acid and washing lotion G are used for joining phosphoric acid solution and recycle.
The new method iron filings phosphoric acid hydrogen peroxide direct replacement that for the present invention, iron filings, phosphoric acid, lithium hydroxide are prepared the ferrous salt of phosphoric acid positive electrode of lithium is oxidized produces high ferric phosphate cheaply, then to the advanced row material by wet type mixing of lithium hydroxide phosphate dihydrate iron pyrolysis carbon source again with pyrocarbon reduction lithium ferrous iron processed salt of phosphoric acid, obtain with nano microcrystalline particle by the evenly ferrous salt of phosphoric acid of submicron particle powder lithium coated and bridging of RESEARCH OF PYROCARBON, the ferrous salt of phosphoric acid tap density of this lithium is higher and more even, the electric conductivity having had and chemical property.
Brief description of the drawings
Fig. 1 is 2FePO prepared by embodiment 1
42H
2the X-ray diffracting spectrum of O.
Fig. 2 is LiFePO prepared by embodiment 1
4x-ray diffracting spectrum.
Fig. 3 is the LiFePO of preparation
4the 18650 type 1200mAh cylindrical lithium ion battery 1C chargings of preparing as positive electrode active material, 0.2C respectively, 1C, 5C discharge curve.
Fig. 4 is the prepared LiFePO of embodiment 1
4the 18650 type 1200mAh cylindrical lithium ion battery 1C chargings of preparing as positive electrode active material, 10C discharge cycles curve.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
The first step: first precipitate legal system phosphate dihydrate iron with solution oxide again with the ferrous phosphate dihydrogen salt solution of iron filings phosphoric acid solution system.
Waste iron filing: battery industry is produced the waste iron filing of hardware factory of cell device, porous scrap iron band, material is as the BDCK of Baosteel or SPCC: wherein only manganese slightly high (Mn≤0.3%) of impurities, but manganese is harmless useful doped chemical.
Waste iron filing is filled to retort from top-feed mouth, and 3.1 mol/L phosphoric acid solutions add reactor to enable entirely to soak iron filings, and 3.1 mol/L phosphoric acid solutions are that commercially available 85% phosphoric acid and water are mixed according to volume ratio 1:3.7; Chuck heating, makes temperature of reactor remain on 50～60 DEG C following displacement reaction is comparatively fast carried out:
Fe+2H
3PO
4=Fe（H
2PO
4）
2+H
2↑ (1)
In the time that reaction speed is slack-off, be progressively heated to 70 DEG C to promote reaction, the hydrogen that reaction produces is from the logical outdoor emptying of reactor head blast pipe, in pipe, condensed water flows back to retort, in the time also substantially not producing hydrogen for 70 DEG C, think and reacted, now pH value=1.5 of test reaction liquid, proportion=1.31, all put into oxidation tank by hot reactant liquor through filter screen, in oxidation tank, the phosphate dihydrogen salt solution A of iron is through chemical analysis: Fe1.3357mol/L, PO
43.2314mol/L; After the supplementary iron filings of retort, add enough phosphoric acid solutions and carry out next round displacement reaction.
In dilution oxidation tank, solution, to its pH value=2.5, adds ferrous white ferric phosphate (phosphate dihydrate iron) the pressed powder deposit B (adding at any time water in oxidizing process keeps pH to be greater than 2) that generates of biphosphate in hydrogen peroxide direct oxidation solution under stirring energetically:
2Fe（H
2PO
4）
2+H
2O
2+2H
2O=2FePO
4·2H
2O↓+2H
3PO
4……(2)
In the time that proceeding in solution without ferrous ion (checking with the potassium ferricyanide), oxidation thinks that precipitation completely, change slow stirring and be heated to 80 DEG C of insulation crystallizations 10 hours, phosphate dihydrate iron powder B is carried out to centrifugation washing with the mother liquor that contains accessory substance phosphoric acid, finish less than ferric ion (checking with potassium ferrocyanide) time when checking in washing lotion, mother liquor and washing lotion are used for joining phosphoric acid,diluted and recycle, and isolated phosphate dihydrate iron powder B is not dried and directly entered next step;
Second step: to the advanced row material by wet type mixing of lithium hydroxide phosphate dihydrate iron pyrolysis carbon source again with pyrocarbon reduction lithium ferrous iron processed salt of phosphoric acid:
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, join the aqueous solution of 1.02 moles of hydrogen lithias and 20 grams of sucrose by every mole of phosphate dihydrate iron (in phosphorus), and the phosphate dihydrate iron powder that will wet under stirring energetically all adds, suspension-turbid liquid C stirs to obtain, by dry suspension-turbid liquid C spraying high ferric phosphate crystallite by the precursor D of sucrose and lithium hydroxide molecular film parcel, precursor D (100 parts by volume decomposed ammonias and 100 parts by volume nitrogen) 500 DEG C of roastings 6 hours under weakly reducing atmosphere, 700 DEG C of roastings 12 hours, at 700 DEG C, roasting net reaction 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 is 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 of made lithium X-ray diffracting spectrum, and Fig. 3 and Fig. 4 are the ferrous salt of phosphoric acid positive electrode of made lithium chemical property figure.
The first step: first precipitate legal system phosphate dihydrate iron with solution oxide again with the ferrous phosphate solution of iron filings phosphoric acid solution system;
Waste iron filing: battery industry is produced the waste iron filing of hardware factory of cell device, porous scrap iron band, material is as the BDCK of Baosteel or SPCC: wherein only manganese slightly high (Mn≤0.3%) of impurities, but manganese is harmless useful doped chemical.
Waste iron filing is filled to retort from top-feed mouth, and 2.7 mol/L phosphoric acid solutions add reactor to enable entirely to soak iron filings, and 2.7 mol/L phosphoric acid solutions are that commercially available 85% phosphoric acid and water are mixed according to volume ratio 1:4.4; Chuck heating, makes temperature of reactor remain on 50～60 DEG C following displacement reaction is comparatively fast carried out:
Fe+2H
3PO
4=Fe（H
2PO
4）
2+H
2↑ (1)
In the time that reaction speed is slack-off, be progressively heated to 70 DEG C to promote reaction, the hydrogen that reaction produces is from the logical outdoor emptying of reactor head blast pipe, in pipe, condensed water flows back to retort, in the time also substantially not producing hydrogen for 70 DEG C, think and reacted, now pH value=3 of test reaction liquid, proportion=1.28, all put into oxidation tank by hot reactant liquor through filter screen, in oxidation tank, the phosphate dihydrogen salt solution A of iron is through chemical analysis: Fe1.2957mol/L, PO
43.1822mol/L; After the supplementary iron filings of retort, add enough phosphoric acid solutions and carry out next round displacement reaction.
Under stirring energetically, add ferrous phosphate (phosphate dihydrate iron) the pressed powder deposit B (adding at any time water in oxidizing process keeps pH to be greater than 2) that generates white iron of biphosphate in hydrogen peroxide direct oxidation solution:
2Fe（H
2PO
4）
2+H
2O
2+2H
2O=2FePO
4·2H
2O↓+2H
3PO
4……(2)
In the time that proceeding in solution without ferrous ion (checking with the potassium ferricyanide), oxidation thinks that precipitation completely, change slow stirring and be heated to 80 DEG C of insulation crystallizations 6 hours, phosphate dihydrate iron powder B is carried out to centrifugation washing with the mother liquor that contains accessory substance phosphoric acid, finish less than ferric ion (checking with potassium ferrocyanide) time when checking in washing lotion, mother liquor and washing lotion are used for joining phosphoric acid,diluted and recycle, and isolated phosphate dihydrate iron powder B is not dried and directly entered next step;
Second step: to the advanced row material by wet type mixing of lithium hydroxide phosphate dihydrate iron pyrolysis carbon source again with pyrocarbon reduction lithium ferrous iron processed salt of phosphoric acid,
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 of 1.00 moles of hydrogen lithias and 23.5 grams of sucrose by every mole of phosphate dihydrate iron (in phosphorus), and the phosphate dihydrate iron powder that will wet under stirring energetically all adds, suspension-turbid liquid C stirs to obtain, by dry suspension-turbid liquid C spraying high ferric phosphate crystallite by the precursor D of sucrose and lithium hydroxide molecular film parcel, precursor D (5 parts by volume hydrogen and 95 parts by volume argon gas) 450 DEG C of roastings 12 hours under weakly reducing atmosphere, 750 DEG C of roastings 8 hours, at 750 DEG C, roasting net reaction 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 electron conduction network of nano microcrystalline embedding RESEARCH OF PYROCARBON formation.
Embodiment 3
The first step: first precipitate legal system phosphate dihydrate iron with solution oxide again with the ferrous phosphate solution of iron filings phosphoric acid solution system;
Waste iron filing: battery industry is produced the waste iron filing of hardware factory of cell device, porous scrap iron band, material is as the BDCK of Baosteel or SPCC: wherein only manganese slightly high (Mn≤0.3%) of impurities, but manganese is harmless useful doped chemical.
Waste iron filing is filled to retort from top-feed mouth, and 2.9 mol/L phosphoric acid solutions add reactor to enable entirely to soak iron filings, and 2.9 mol/L phosphoric acid solutions are that commercially available 85% phosphoric acid and water are mixed according to volume ratio 1:4.0; Chuck heating, makes temperature of reactor remain on 50～60 DEG C following displacement reaction is comparatively fast carried out:
Fe+2H
3PO
4=Fe（H
2PO
4）
2+H
2↑ (1)
In the time that reaction speed is slack-off, be progressively heated to 70 DEG C to promote reaction, the hydrogen that reaction produces is from the logical outdoor emptying of reactor head blast pipe, in pipe, condensed water flows back to retort, in the time also substantially not producing hydrogen for 70 DEG C, think and reacted, now pH value=2 of test reaction liquid, proportion=1.30, all put into oxidation tank by hot reactant liquor through filter screen, in oxidation tank, the phosphate dihydrogen salt solution A of iron is through chemical analysis: Fe1.3208mol/L, PO
43.1905mol/L; After the supplementary iron filings of retort, fill up phosphoric acid solution and carry out next round displacement reaction.
Under stirring energetically, add ferrous phosphate (phosphate dihydrate iron) the pressed powder deposit B (adding at any time water in oxidizing process keeps pH to be greater than 2) that generates white iron of biphosphate in hydrogen peroxide direct oxidation solution:
2Fe（H
2PO
4）
2+H
2O
2+2H
2O=2FePO
4·2H
2O↓+2H
3PO
4……(2)
It is because there is accessory substance phosphoric acid to generate [seeing reaction equation (2)] in oxidizing process that oxidizing process keeps pH to be greater than 2, and phosphoric acid acidity Fe(H when large
2pO
4)
2ferrous ion oxidation may be incomplete, and ferric iron can be with Fe(H
2pO
4)
3state exists and in solution, makes FePO
42H
2o precipitation not exclusively, in the time that proceeding in solution without ferrous ion (checking with the potassium ferricyanide), oxidation thinks that precipitation completely, change slow stirring and be heated to about 70～80 DEG C insulation crystallizations 12 hours, phosphate dihydrate iron powder B is carried out to centrifugation washing with the mother liquor that contains accessory substance phosphoric acid, finish less than ferric ion (checking with potassium ferrocyanide) time when checking in washing lotion, mother liquor and washing lotion are used for joining phosphoric acid,diluted and recycle, and isolated phosphate dihydrate iron powder B is not dried and directly entered next step;
Second step: to the advanced row material by wet type mixing of lithium hydroxide phosphate dihydrate iron pyrolysis carbon source again with pyrocarbon reduction lithium ferrous iron processed salt of phosphoric acid,
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 of 1.04 moles of hydrogen lithias and 32.8 grams of sucrose by every mole of phosphate dihydrate iron (in phosphorus), and the phosphate dihydrate iron powder that will wet under stirring energetically all adds, suspension-turbid liquid C stirs to obtain, by dry suspension-turbid liquid C spraying high ferric phosphate crystallite by the precursor D of sucrose and lithium hydroxide molecular film parcel, precursor D (15 parts by volume hydrogen and 85 parts by volume nitrogen) 500 DEG C of roastings 4 hours under weakly reducing atmosphere, 680 DEG C of roastings 20 hours, at 680 DEG C, roasting net reaction 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 electron conduction network of nano microcrystalline embedding RESEARCH OF PYROCARBON formation.
Above embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various distortion and improvement that the common engineers and technicians in this area make technical scheme of the present invention, all should fall in the definite protection range of claims of the present invention.
Claims (3)
1. the method for preparing the ferrous salt of phosphoric acid positive electrode of lithium with iron filings, phosphoric acid, lithium hydroxide, comprises the steps:
Phosphoric acid solution reacts with iron filings, in the time of pH value >=1.5 of reactant liquor or proportion 1.28～1.31, collect and contain the reaction solution A of ferrous dihydric phosphate and transfer in oxidation tank, regulate pH value to be greater than 2, under agitation add hydrogen peroxide ferrous dihydric phosphate is oxidized to phosphate dihydrate iron and accessory substance phosphoric acid, add supplementing water in hydrogen peroxide process and be greater than 2 with maintenance pH;
When adding while producing without white precipitate in solution after hydrogen peroxide, slowly stir and heating crystallization, by Crystallization Separation washing, obtain white phosphate dihydrate iron pressed powder B and mother liquor and washing lotion G containing accessory substance phosphoric acid;
Pressed powder B is evenly mixed to get suspension-turbid liquid C with the lithium hydroxide solution containing pyrolysis carbon source;
The dry high ferric phosphate crystallite that obtains of suspension-turbid liquid C spraying is by the precursor D of sucrose and lithium hydroxide molecular film parcel;
Described precursor D carries out two-stage roasting under reducing atmosphere, and first paragraph is 450～500 DEG C, and second segment is 650～750 DEG C, 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;
Described phosphoric acid solution is 3.1,2.7 or 2.9 mol/L;
The described phosphoric acid phosphoric acid solution that to be commercially available 85% phosphoric acid and water be mixed according to volume ratio 1:3.7 or 1:4.4 or 1:4.0;
The temperature that described phosphoric acid solution reacts with described iron filings remains on 50～70 DEG C;
The mol ratio of described white phosphate dihydrate iron pressed powder B, described lithium hydroxide, described RESEARCH OF PYROCARBON is (1.00): (1.00～1.05): (0.70～1.16);
Described reducing atmosphere is under the mist condition of percent by volume 5～15% hydrogen and percent by volume 95～85% nitrogen or argon gas or under the mist condition of 100 parts of decomposed ammonias and 400～67 parts of nitrogen or argon gas;
Described hydrogen peroxide concentration is 27.5%.
2. method according to claim 1, is characterized in that: described pyrolysis carbon source be selected from sucrose, glucose, citric acid, starch and polyvinyl alcohol any or appoint several.
3. method according to claim 1, is further characterized in that: the described mother liquor containing accessory substance phosphoric acid and washing lotion G are used for joining phosphoric acid solution and recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010553079.2A CN102464309B (en) | 2010-11-19 | 2010-11-19 | Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010553079.2A CN102464309B (en) | 2010-11-19 | 2010-11-19 | Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102464309A CN102464309A (en) | 2012-05-23 |
| CN102464309B true CN102464309B (en) | 2014-06-11 |
Family
ID=46068480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010553079.2A Expired - Fee Related CN102464309B (en) | 2010-11-19 | 2010-11-19 | Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102464309B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817059B (en) * | 2015-04-29 | 2017-07-18 | 江西东华科技园有限责任公司 | A kind of method that battery-grade iron phosphate is prepared by iron powder and phosphatase reaction |
| CN105480960B (en) * | 2015-12-29 | 2018-10-19 | 河北斯霖百特新能源科技有限公司 | Ferric 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 |
| CN107863531B (en) * | 2017-11-03 | 2020-04-28 | 山东科技大学 | Method for preparing lithium ion battery anode material by using siderite |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101237043A (en) * | 2008-01-31 | 2008-08-06 | 东北师范大学 | Method for making ferrous lithium phosphate/carbon compound material of high active disorderly ferric phosphate |
| CN101355158B (en) * | 2008-09-17 | 2010-11-17 | 长沙矿冶研究院 | Lithium ion battery anode material LiFePO4Preparation method of (1) |
| CN102447099B (en) * | 2010-10-09 | 2014-01-29 | 河南环宇集团有限公司 | New method for preparing lithium ferrous phosphate double-salt anode material by using iron chippings, phosphoric acid and lithium hydroxide |
-
2010
- 2010-11-19 CN CN201010553079.2A patent/CN102464309B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102464309A (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102464309B (en) | Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide | |
| CN100420075C (en) | Method for preparing lithium ion battery anode material lithium ion phosphate | |
| CN109473657A (en) | A kind of nickel cobalt aluminium manganese quaternary lithium-ion battery positive electrode material being mixed with, Preparation method and use | |
| CN113526483B (en) | Ferro-phosphorus sodalite type cathode material and preparation method and application thereof | |
| US9932235B2 (en) | Preparation method of battery composite material and precursor thereof | |
| CN104393256B (en) | The preparation method of LiFePO4 phosphoric acid vanadium lithium/carbon In-situ reaction positive electrode | |
| CN110931781A (en) | Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material | |
| CN103435104B (en) | A kind of preparation method of lithium ion battery negative electrode material-nano zinc ferrite | |
| CN102709533A (en) | Preparation method of lithium sulphur battery anode material with high power and high specific capacity | |
| CN109665570A (en) | A kind of nickelic quaternary positive electrode, the Preparation method and use of doping vario-property | |
| CN103996852A (en) | Preparation method of novel nano lithium vanadium phosphate positive electrode material | |
| CN102832391A (en) | Method for preparing LiFe[x]M[1-x]PO4/C lithium ion composite anode material | |
| CN102479944B (en) | Preparation method and application of lithium iron phosphate composite material | |
| CN105958020A (en) | Method for preparing nanometer FeF<3>.0.33H<2>O by alcohol-thermal method | |
| CN100483809C (en) | Method for producing ultra-fine LiFePO4/C of lithium ion battery anode material | |
| CN102447099B (en) | New method for preparing lithium ferrous phosphate double-salt anode material by using iron chippings, phosphoric acid and lithium hydroxide | |
| CN104009221B (en) | Method for preparing positive electrode material rich in lithium via sol-gel self-propagating combustion method | |
| CN107785570B (en) | Preparation method for improving yield of olivine structure electrode material by hydrothermal method | |
| CN111048753B (en) | Iron oxide doped phosphorus atom composite material and preparation method and application thereof | |
| CN102569791A (en) | Lithium iron phosphate with flower-like structure and preparation method thereof | |
| CN101969117A (en) | Preparation method of lithium ion battery cathode material coated with carbon on surface | |
| CN100389062C (en) | Method for preparing composite material of carbon coated lithium ferrous phosphate through iron phosphate | |
| CN102437335B (en) | Method for coating lithium ion battery anode material LiFePO4 by self-segregation of aluminum | |
| CN103011116B (en) | Produce the method for anode material for lithium-ion batteries amorphous precursors | |
| CN102412399B (en) | A kind of preparation method of manganese phosphate lithium front body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20150331 Granted publication date: 20140611 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20160331 Granted publication date: 20140611 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20160922 Granted publication date: 20140611 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20170322 Granted publication date: 20140611 |
|
| PP01 | Preservation of patent right |
Effective date of registration: 20170515 Granted publication date: 20140611 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20180515 Granted publication date: 20140611 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140611 Termination date: 20181119 |