CN104805299B - Method for preparing lithium battery electrode materials LiFePO4 and Li4Ti5O12 from vanadium extraction slag - Google Patents
Method for preparing lithium battery electrode materials LiFePO4 and Li4Ti5O12 from vanadium extraction slag Download PDFInfo
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- CN104805299B CN104805299B CN201510176302.9A CN201510176302A CN104805299B CN 104805299 B CN104805299 B CN 104805299B CN 201510176302 A CN201510176302 A CN 201510176302A CN 104805299 B CN104805299 B CN 104805299B
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- gained
- leachate
- vanadium extraction
- lithium
- lifepo4
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 107
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000000605 extraction Methods 0.000 title claims abstract description 85
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 67
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 61
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007772 electrode material Substances 0.000 title claims abstract description 14
- 239000002893 slag Substances 0.000 title abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 109
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 93
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 51
- 239000002243 precursor Substances 0.000 claims abstract description 51
- 239000010936 titanium Substances 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 46
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 42
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- -1 titanium peroxide compound Chemical class 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 239000010406 cathode material Substances 0.000 claims abstract description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims abstract description 5
- 239000002699 waste material Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 47
- 239000005955 Ferric phosphate Substances 0.000 claims description 35
- 229940032958 ferric phosphate Drugs 0.000 claims description 35
- 238000001354 calcination Methods 0.000 claims description 33
- 238000002386 leaching Methods 0.000 claims description 29
- 239000007774 positive electrode material Substances 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 25
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 25
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 238000004176 ammonification Methods 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000012467 final product Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910009866 Ti5O12 Inorganic materials 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000010025 steaming Methods 0.000 claims description 12
- 239000013589 supplement Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 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 5
- 229920001817 Agar Polymers 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000008272 agar Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000011435 rock Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 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 3
- 239000008103 glucose Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 238000002845 discoloration Methods 0.000 claims 1
- 235000013312 flour Nutrition 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 3
- 229910000901 LiFePO4/C Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 229910010710 LiFePO Inorganic materials 0.000 description 24
- 239000000463 material Substances 0.000 description 22
- 229960002163 hydrogen peroxide Drugs 0.000 description 12
- 239000011261 inert gas Substances 0.000 description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 11
- 229910021487 silica fume Inorganic materials 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 230000008901 benefit Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing lithium battery electrode materials LiFePO4 and Li4Ti5O12 from vanadium extraction slag. The method comprises the following steps: (1), iron and titanium separation: the vanadium extraction slag is leached with hydrochloric acid and filtered to obtain iron-rich leached filtrate and titanium-rich leached residues; (2), preparation of a LiFePO4 precursor: phosphoric acid is added to the iron-rich leached filtrate, H2O2 and ammonia water are added, and the mixture is precipitated, filtered and dried to obtain FePO4 powder; (3) preparation of a LiFePO4 lithium secondary battery cathode material: the FePO4 precursor, Li2CO3 and an organic carbon source are mixed and calcined to obtain LiFePO4/C; (4) preparation of a Li4Ti5O12 precursor: NH3*H2O is added to the titanium-rich leached residues, the mixture is heated, then H2O2, ammonia water and concentrated H2SO4 are added, and filtrate is subjected to heating reaction and evaporated to dryness to obtain a titanium peroxide compound; (5), preparation of Li4Ti5O12 lithium secondary battery anode material: the titanium peroxide compound is calcined to obtain TiO2, and TiO2 and Li2CO3 are mixed and calcined to obtain Li4Ti5O12. Valuable elements of the vanadium extraction slag are wholly used to acquire a high added-value product, and efficient vanadium extraction slag utilization and environmental protection are realized.
Description
Technical field
The present invention relates to forerunner's body method of lithium ion battery electrode material is and in particular to vanadium extraction waste prepares lithium battery
Pole material ferric lithium phosphate and the method for lithium titanate.
Background technology
In recent years, the LiFePO4 of olivine structural is because having theoretical specific capacity height (170mAh 〃 g-1), good cycle,
Heat endurance is good, cheap, advantages of environment protection, becomes one of the most promising anode material for lithium-ion batteries.
The lithium titanate of spinel structure has excellent structural stability (lithium ion deintercalation process " zero strain ") and security performance because of it
(Li4Ti5O12:Li/Li relativelyTenReduction potential be 1.5V, lithium metal can be avoided to separate out) it is considered to be a kind of good Gao Gong
Rate lithium ion battery and asymmetric hybrid battery negative material.The quality of lithium titanate and LiFePO4 performance is largely fixed
In the quality of its presoma, prepare LiFePO4 at present and the presoma of lithium titanate is mostly high-purity molysite or titanium salt.These are former
Material major part is to be obtained through a series of removal of impurities operation by ore, and prepares LiFePO4 and lithium titanate with these high pure raw materials
When need to add some doped chemicals beneficial to its chemical property (as Mg, Mn, Nb, Cr etc.) again, these doped chemicals are most
Natural minerals there is, thus leading to flow process to repeat, cost greatly increases.Therefore, mineral (or waste material) are directly utilized to make
The presoma of standby lithium ion battery electrode material is the effective ways reducing its production cost.
On the other hand, China's vanadium titano-magnetite aboundresources, widely distributed, after reserves are located at South Africa and Russia, occupies
Third place in the world, is mainly distributed on Sichuan, Chengde area.In v-bearing steel slag, calcium, iron content are high, and content of vanadium is low,
Occurrence patterns are complicated, and recycling difficulty is very big, and from slag, vanadium extraction remains a global difficult problem at present.Except continuing to carry
Vanadium, at present, the recycling containing vanadium solid waste also has two big class：As functionality ceramic raw material and cement raw material.The former as above-mentioned with
Vanadium titano-magnetite is that the vanadium extraction waste of raw material is mainly former as preparation feature or ornamental ceramic black ceramic colorant
Material, the latter is to be used as cement mixture with stone coal mine for raw material vanadium-extracted residues.Although method utilized above is whole utilization, real
The effect of a part of composition in waste all be with only on border, added value is not high, and particularly Ti resource utilization is very low.And with
Meaning heap is abandoned, and wherein the dissociation diffusion potential of the poisonous ion of the heavy metal such as vanadium, chromium must cause direct pollution and great calamity to environment
Evil hidden danger.
Content of the invention
Brief overview with regard to the present invention is given below, to provide the basic reason with regard to certain aspects of the invention
Solution.It should be appreciated that this general introduction is not the exhaustive general introduction with regard to the present invention.It is not intended to determine the key of the present invention
Or pith, nor is it intended to limit the scope of the present invention.Its purpose only provides some concepts in simplified form, with
This is as the preamble in greater detail discussed after a while.
The purpose of the embodiment of the present invention is the defect for above-mentioned prior art, provides a kind of environmentally friendly, solid to give up
The method that thing resource and the high vanadium extraction waste of added value utilization rate prepare electrode material of lithium battery LiFePO4 and lithium titanate.
To achieve these goals, the present invention adopts the technical scheme that：
A kind of vanadium extraction waste electrode material of lithium battery LiFePO4 and the method for lithium titanate, comprise the following steps：
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, with salt Ore Leaching vanadium extraction waste, it is filtrated to get Fu Tie after the completion of leaching and leaches filter
Liquid and rich titanium leach filter residue；
(2) prepare ferric lithium phosphate precursor：
Leach free HCl in filtrate to step (1) gained richness iron to carry out steaming acid recovery process, obtain concentrating leachate, join
Make rich iron leachate；By precipitating reagent phosphoric acid H3PO4Add in rich iron leachate, add oxidant hydrogen peroxide H2O2Stirring is anti-
Should, ammonification water adjusts solution system pH value, reacts further, and gained precipitation filters and washing and drying, that is, before obtaining LiFePO4
Drive body ferric phosphate FePO4Powder；
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
Ferric phosphate FePO by gained in step (2)4Presoma and Li2CO3And organic carbon source mixes, in atmosphere furnace
Calcine under middle inert gas shielding, take out after cooling, that is, obtain LiFePO4/ C positive electrode material；
(4) prepare lithium titanate precursor：
Filter residue is leached to gained richness titanium in step (1) and adds NH3·H2O, heats and stirs, add H2O2, adding
H2O2During constantly dropping ammoniacal liquor adjust pH value, be subsequently adding dense H2SO4Continue reaction, filter out filtrate, will be anti-for filtrate heating
Should, lighter, to milky, is evaporated and obtains faint yellow xerogel, as lithium titanate precursor peroxide titanium compound；Filter
Slag is SILICA FUME；
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined, obtains TiO2Powder；By TiO2Powder and Li2CO3Mix,
In the air is calcined, and obtains final product lithium titanate Li after along with the furnace cooling4Ti5O12Negative electrode material powder.
In described step (1)：Leach vanadium extraction waste, hydrochloric acid and vanadium extraction with the hydrochloric acid of mass concentration 15-35% at ambient pressure
The mass ratio of waste is 1.5-3.0,70-110 DEG C of extraction temperature, and extraction time is 1-5h；Will be cold for gained slurry after the completion of leaching
But to room temperature, then filtered.
In described step (2)：Concentrate the rich iron leachate that leachate is configured to 0.2-0.8 molar concentration；Ammonification water is adjusted
Solution system pH value is 2-4；
After adding phosphoric acid, after 30-70 DEG C of heating stirring 0.5-1h, add oxidant stirring reaction 5-30min；Ammonification water
Continue reaction 1-5h afterwards；
Wherein, in solution, divalence Fe mole and the addition of precipitating reagent are Fe/P mol ratio 0.75-1：1, oxidant
Addition is 0.45-0.55 times of divalence Fe mole in solution.
In described step (3)：In described step (3)：Described ferric phosphate FePO4Presoma and Li2CO3And organic carbon source
Mol ratio 2:1：(0.5～1)；
In described atmosphere furnace, the temperature of calcining is 700-800 DEG C, and calcination time is 8-15h.
In described step (4)：
In 30-70 DEG C of heating stirring to assuming white suspension after adding 12.5wt% weak aqua ammonia, continue dropping
It is 4-8 that 12.5wt% weak aqua ammonia adjusts pH value, then under vigorous stirring, leaches filter residue by every gram of rich titanium and adds 2-6mlH2O2,
Supplement ammoniacal liquor and stablize pH value to setting value, add dense H2SO4It is in orange-yellow to suspension, continue reaction 0.5-1.5h, be filtrated to get
Leachate, 90-110 DEG C of heating of leachate is evaporated, obtains peroxide titanium compound.
In described step (5)：
The calcining heat of described peroxide titanium compound is 400-600 DEG C of calcining 3-5h；Described TiO2Powder and Li2CO3Press
Li:Ti mol ratio 4:5 mix, and described in the air calcining heat is 750-850 DEG C, and calcination time is 5-10h.
Described LiFePO4 LiFePO4Organic carbon source used by positive electrode material of lithium secondary cell is selected from glucose, starch, sugarcane
At least one in sugar, agar powder, gelatin, citric acid and rock sugar.
The present invention also provides a kind of electrode material of lithium battery LiFePO4 and lithium titanate, is prepared into according to above-mentioned method
Arrive.
Compared with prior art, the invention has the beneficial effects as follows：
It is raw material that the present invention make use of vanadium extraction waste this industry bulk solid waste well, simultaneously synthesizing two kinds of lithiums
The presoma of the electrode material of battery, i.e. the presoma ferrous acid lithium of LiFePO 4 of anode material, and negative material metatitanic acid
The presoma titanium dioxide of lithium, prepares LiFePO4 LiFePO further4Positive electrode and lithium titanate Li4Ti5O12Negative pole material
Material.In vanadium extraction waste in preparation process, other minor metallic elements in addition to iron, titanium (aluminium, magnesium, manganese etc.) are evenly distributed on forerunner
In body crystal grain, make need not adulterate again during synthesis subsequent electrode material, these doped chemicals can greatly improve LiFePO4 and metatitanic acid
The chemical property of lithium.Therefore, the invention is particularly suited to being lithium ion battery anode material lithium iron phosphate and negative material titanium
The production of sour lithium provides the cheap source of iron of high-quality and titanium source, fully achieves the efficient and sustainable profit of vanadium extraction waste each element
With, it is to avoid environmental pollution, added value utilization rate is high, is that large-scale production brings huge economic benefit and environmental protection society effect
Benefit.
Brief description
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Have technology description in required use accompanying drawing be briefly described it should be apparent that, drawings in the following description be only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, also may be used
So that other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the electrode material LiFePO preparing lithium secondary battery from vanadium extraction waste4And Li4Ti5O12Technological process
Figure；
Fig. 2 a is LiFePO in embodiment 14SEM (Scanning Electron Microscope, scanning electron microscopy
Mirror) figure；
Fig. 2 b is Li in embodiment 14Ti5O12SEM figure；
Fig. 3 a is LiFePO in embodiment 24SEM figure；
Fig. 3 b is Li in embodiment 24Ti5O12SEM figure；
Fig. 4 a is LiFePO in embodiment 34SEM figure；
Fig. 4 b is Li in embodiment 34Ti5O12SEM figure；
Fig. 5 a is LiFePO in embodiment 44SEM figure；
Fig. 5 b is Li in embodiment 44Ti5O12SEM figure；
Fig. 6 a is LiFePO in embodiment 54SEM figure；
Fig. 6 b is Li in embodiment 54Ti5O12SEM figure；
Fig. 7 a is LiFePO in embodiment 64SEM figure；
Fig. 7 b is Li in embodiment 64Ti5O12SEM figure；
Fig. 8 a is LiFePO in embodiment 74SEM figure；
Fig. 8 b is Li in embodiment 74Ti5O12SEM figure；
Fig. 9 a is LiFePO in embodiment 84SEM figure；
Fig. 9 b is Li in embodiment 84Ti5O12SEM figure；
Figure 10 a is LiFePO in embodiment 94SEM figure；
Figure 10 b is Li in embodiment 94Ti5O12SEM figure；
Figure 11 a is LiFePO in embodiment 104SEM figure；
Figure 11 b is Li in embodiment 104Ti5O12SEM figure.
Specific embodiment
Purpose, technical scheme and advantage for making the embodiment of the present invention are clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described it is clear that described embodiment is
The a part of embodiment of the present invention, rather than whole embodiments.Described in the accompanying drawing of the present invention or a kind of embodiment
Element and feature can with one or more other accompanying drawings or embodiment shown in element and feature combine.Should
Note, for purposes of clarity, eliminate unrelated to the invention, known to persons of ordinary skill in the art in accompanying drawing and explanation
Part and the expression processing and description.Based on the embodiment in the present invention, those of ordinary skill in the art are not paying creation
Property work under the premise of the every other embodiment that obtained, broadly fall into the scope of protection of the invention.
Referring to Fig. 1, a kind of method preparing LiFePO4 and lithium titanate using vanadium extraction waste.Comprise the following steps：
(1) ferrotitanium separates：By vanadium extraction waste Mechanical Crushing, with salt Ore Leaching vanadium extraction waste, separation of solid and liquid is filtrated to get richness
Iron leachate and rich titanium leached mud；
(2) preparation of ferric lithium phosphate precursor ferric phosphate：With leachate as raw material, using H3PO4Prepared by selective precipitation
Ferric phosphate.H by certain mol proportion example3PO4Solution is added to out in liquid, strong agitation, adds a certain amount of hydrogen peroxide, makes Fe
(II) all it is oxidized to Fe (III), finally adjust pH value, isothermal reaction with ammoniacal liquor, gained precipitation filters and washing and drying, obtains final product
To ferric phosphate powder body.
(3) preparation of LiFePO4：With ferric phosphate as raw material, LiFePO is synthesized using carbothermic method4The secondary electricity of/C lithium
Pond positive electrode.Stoichiometrically weigh Li2CO3, presoma and organic carbon source, mix, inert gas in atmosphere furnace
Protection is lower to calcine, and takes out after cooling, that is, obtains containing LiFePO metal-doped on a small quantity4/ C positive electrode material.
(4) in H2O2—NH3〃H2O—H2SO4System, carries out Selectively leaching to the titanium in leached mud, obtains titanium peroxide
Compound, prepares TiO2And Li4Ti5O12Negative material.
The each valuable element of whole utilization vanadium extraction waste of the present invention, synthesizes lithium battery material LiFePO4And Li4Ti5O12Contour attached
Value-added product is it is achieved that the efficient utilization of vanadium extraction waste and environmental protection.
The ferric lithium phosphate precursor ferric phosphate FePO of the present invention4Raw material be vanadium extraction waste iron leachate.Before lithium titanate
Driving body peroxide titanium compound is in sour environment, uses H2O2—NH3〃H2O system leaches the titanium in filter residue to rich titanium and selects
The leaching of selecting property obtains.
The present invention, with intractable multiple water logging vanadium extraction waste as raw material, prepares lithium-ion electric with selective precipitation technology
Pond lithium titanate of negative pole material and LiFePO 4 of anode material presoma, and then low cost preparation both lithium ion batteries are positive and negative
Pole material LiFePO4And Li4Ti5O12, realize environmental friendliness, reclamation of solid wastes and high value added utilization.
Below by specific embodiment, the present invention is further illustrated：
Embodiment 1
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 15%, hydrochloric acid with
The mass ratio of vanadium extraction waste is 2.125,70 DEG C of extraction temperature, and extraction time is 2h；After the completion of leaching, gained slurry is cooled to
Room temperature, is filtrated to get Fu Tie and leaches filtrate and rich titanium leaching filter residue.
(2) prepare ferric lithium phosphate precursor ferric phosphate：
HCl free in step (1) gained leachate is carried out steaming acid recovery process, obtains concentrating leachate, be configured to
The rich iron leachate of 0.265 molar concentration.It is 0.75 by Fe/P mol ratio, by phosphoric acid H3PO4Add in rich iron leachate, 30 DEG C
After heating stirring 0.5h, add the oxydol H of 0.45 times of ferrous iron mole2O2Stirring reaction 10min, ammonification water adjusts molten
Liquid system pH value is 2, reacts 1h further, gained precipitation filters and washing and drying, that is, obtain ferric lithium phosphate precursor phosphorus
Sour iron FePO4Powder.
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
2.265g ferric phosphate FePO by gained in step (2)4With 0.555gLi2CO3And the mixing of 1.353g glucose is all
Even, under inert gas shielding in atmosphere furnace, 700 DEG C of calcining 8h, take out after cooling, that is, obtain LiFePO4/ C positive electrode material.
(4) prepare lithium titanate precursor peroxide titanium compound：
Step (1) gained richness titanium is leached white to presenting in 30 DEG C of heating stirrings after addition 12.5wt% weak aqua ammonia in filter residue
Color suspension, continue dropping 12.5wt% weak aqua ammonia to adjust pH value is 4, then under vigorous stirring, leaches filter by every gram of rich titanium
Slag adds 2mlH2O2, supplement ammoniacal liquor and stablize pH value to 4, add dense H2SO4It is in orange-yellow to suspension, continue reaction 1h, filter
Obtain leachate, 100 DEG C of heating of leachate are evaporated, obtain faint yellow xerogel, as lithium titanate precursor peroxide titanizing
Compound.Crossing filter residue is SILICA FUME.
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined 4h in 500 DEG C, obtains TiO2Powder；By 6gTiO2With
2.22gLi2CO3Mix, 750 DEG C of calcining 5h of in the air, after along with the furnace cooling, obtain final product lithium titanate Li4Ti5O12Negative material powder
Body.
Referring to Fig. 2 a and Fig. 2 b, the respectively LiFePO of the present embodiment gained4And Li4Ti5O12SEM figure.
Embodiment 2
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 20%, hydrochloric acid with
The mass ratio of vanadium extraction waste is 1.75,90 DEG C of extraction temperature, and extraction time is 5h；After the completion of leaching, gained slurry is cooled to room
Temperature, is filtrated to get Fu Tie and leaches filtrate and rich titanium leaching filter residue.
(2) prepare ferric lithium phosphate precursor ferric phosphate：
HCl free in step (1) gained leachate is carried out steaming acid recovery process, obtains concentrating leachate, be configured to
The rich iron leachate of 0.528 molar concentration.It is 0.87 by Fe/P mol ratio, by phosphoric acid H3PO4Add in rich iron leachate, 70 DEG C
After heating stirring 1h, add the oxydol H of 0.55 times of ferrous iron mole2O2Stirring reaction 5min, ammonification water adjusts solution body
Be pH value be 4, further react 5h, gained precipitation filter and washing and drying, that is, obtain ferric lithium phosphate precursor ferric phosphate
FePO4Powder.
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
2.265g ferric phosphate FePO by gained in step (2)4With 0.555gLi2CO3And 0.618g starch mixes,
Under inert gas shielding in atmosphere furnace, 800 DEG C of calcining 15h, take out after cooling, that is, obtain LiFePO4/ C positive electrode material.
(4) prepare lithium titanate precursor peroxide titanium compound：
Step (1) gained richness titanium is leached white to presenting in 40 DEG C of heating stirrings after addition 12.5wt% weak aqua ammonia in filter residue
Color suspension, continue dropping 12.5wt% weak aqua ammonia to adjust pH value is 8, then under vigorous stirring, leaches filter by every gram of rich titanium
Slag adds 6mlH2O2, supplement ammoniacal liquor and stablize pH value to 8, add dense H2SO4It is in orange-yellow to suspension, continue reaction 0.5h, mistake
Filter obtains leachate, 90 DEG C of heating of leachate is evaporated, obtains faint yellow xerogel, as lithium titanate precursor peroxide titanizing
Compound.Crossing filter residue is SILICA FUME.
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined 6h in 400 DEG C, obtains TiO2Powder；By 6gTiO2With
2.22gLi2CO3Mix, 850 DEG C of calcining 10h of in the air, after along with the furnace cooling, obtain final product lithium titanate Li4Ti5O12Negative material
Powder.
Referring to Fig. 3 a and Fig. 3 b, the respectively LiFePO of the present embodiment gained4And Li4Ti5O12SEM figure.
Embodiment 3
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 35%, hydrochloric acid with
The mass ratio of vanadium extraction waste is 2.5,110 DEG C of extraction temperature, and extraction time is 1h；After the completion of leaching, gained slurry is cooled to room
Temperature, is filtrated to get Fu Tie and leaches filtrate and rich titanium leaching filter residue.
(2) prepare ferric lithium phosphate precursor ferric phosphate：
HCl free in step (1) gained leachate is carried out steaming acid recovery process, obtains concentrating leachate, be configured to
The rich iron leachate of 0.79 molar concentration.It is 1 by Fe/P mol ratio, by phosphoric acid H3PO4Add in rich iron leachate, 50 DEG C of heating
After stirring 0.8h, add the oxydol H of 0.475 times of ferrous iron mole2O2Stirring reaction 30min, ammonification water adjusts solution body
Be pH value be 3, further react 3h, gained precipitation filter and washing and drying, that is, obtain ferric lithium phosphate precursor ferric phosphate
FePO4Powder.
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
2.265g ferric phosphate FePO by gained in step (2)4With 0.555gLi2CO3, 1.715g sucrose mix,
In atmosphere furnace, the lower 750 DEG C of calcining 10h of inert gas shielding, take out after cooling, that is, obtain LiFePO4/ C positive electrode material.
(4) prepare lithium titanate precursor peroxide titanium compound：
Step (1) gained richness titanium is leached white to presenting in 50 DEG C of heating stirrings after addition 12.5wt% weak aqua ammonia in filter residue
Color suspension, continue dropping 12.5wt% weak aqua ammonia to adjust pH value is 6, then under vigorous stirring, leaches filter by every gram of rich titanium
Slag adds 4mlH2O2, supplement ammoniacal liquor and stablize pH value to 6, add dense H2SO4It is in orange-yellow to suspension, continue reaction 1.5h, mistake
Filter obtains leachate, 110 DEG C of heating of leachate is evaporated, obtains faint yellow xerogel, as lithium titanate precursor peroxide titanium
Compound.Crossing filter residue is SILICA FUME.
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined 4h in 500 DEG C, obtains TiO2Powder；By 6gTiO2With
2.22gLi2CO3Mix, 800 DEG C of calcining 8h of in the air, after along with the furnace cooling, obtain final product lithium titanate Li4Ti5O12Negative material powder
Body.
Referring to Fig. 4 a and Fig. 4 b, the respectively LiFePO of the present embodiment gained4And Li4Ti5O12SEM figure.
Embodiment 4
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 30%, hydrochloric acid with
The mass ratio of vanadium extraction waste is 1.5,100 DEG C of extraction temperature, and extraction time is 3h；After the completion of leaching, gained slurry is cooled to room
Temperature, is filtrated to get Fu Tie and leaches filtrate and rich titanium leaching filter residue.
(2) prepare ferric lithium phosphate precursor ferric phosphate：
HCl free in step (1) gained leachate is carried out steaming acid recovery process, obtains concentrating leachate, be configured to
The rich iron leachate of 0.20 molar concentration.It is 0.80 by Fe/P mol ratio, by phosphoric acid H3PO4Add in rich iron leachate, 40 DEG C add
After thermal agitation 0.6h, add the oxydol H of 0.49 times of ferrous iron mole2O2Stirring reaction 20min, ammonification water adjusts solution
System pH is 2.5, reacts 2h further, gained precipitation filters and washing and drying, that is, obtain ferric lithium phosphate precursor phosphoric acid
Iron FePO4Powder.
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
2.265g ferric phosphate FePO by gained in step (2)4With 0.555gLi2CO3And 0.608g starch and 0.676g Portugal
Grape sugar mixes, and under inert gas shielding in atmosphere furnace, 720 DEG C of calcining 9h, take out after cooling, that is, obtain LiFePO4/C
Positive electrode.
(4) prepare lithium titanate precursor peroxide titanium compound：
Step (1) gained richness titanium is leached white to presenting in 60 DEG C of heating stirrings after addition 12.5wt% weak aqua ammonia in filter residue
Color suspension, continue dropping 12.5wt% weak aqua ammonia to adjust pH value is 5, then under vigorous stirring, leaches filter by every gram of rich titanium
Slag adds 3mlH2O2, supplement ammoniacal liquor and stablize pH value to 5, add dense H2SO4It is in orange-yellow to suspension, continue reaction 1h, filter
Obtain leachate, 100 DEG C of heating of leachate are evaporated, obtain faint yellow xerogel, as lithium titanate precursor peroxide titanizing
Compound.Crossing filter residue is SILICA FUME.
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined 3h in 600 DEG C, obtains TiO2Powder；By 6gTiO2With
2.22gLi2CO3Mix, 760 DEG C of calcining 6h of in the air, after along with the furnace cooling, obtain final product lithium titanate Li4Ti5O12Negative material powder
Body.
Referring to Fig. 5 a and Fig. 5 b, the respectively LiFePO of the present embodiment gained4And Li4Ti5O12SEM figure.
Embodiment 5
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 25%, hydrochloric acid with
The mass ratio of vanadium extraction waste is 3,80 DEG C of extraction temperature, and extraction time is 4h；After the completion of leaching, gained slurry is cooled to room temperature,
It is filtrated to get Fu Tie and leach filtrate and rich titanium leaching filter residue.
(2) prepare ferric lithium phosphate precursor ferric phosphate：
HCl free in step (1) gained leachate is carried out steaming acid recovery process, obtains concentrating leachate, be configured to
The rich iron leachate of 0.35 molar concentration.It is 0.90 by Fe/P mol ratio, by phosphoric acid H3PO4Add in rich iron leachate, 60 DEG C add
After thermal agitation 0.7h, add the oxydol H of 0.52 times of ferrous iron mole2O2Stirring reaction 15min, ammonification water adjusts solution
System pH is 3.5, reacts 4h further, gained precipitation filters and washing and drying, that is, obtain ferric lithium phosphate precursor phosphoric acid
Iron FePO4Powder.
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
2.265g ferric phosphate FePO by gained in step (2)4With 0.555gLi2CO3And 1.285g sucrose and 0.776 Portugal
Grape sugar mixes, and under inert gas shielding in atmosphere furnace, 730 DEG C of calcining 11h, take out after cooling, that is, obtain LiFePO4/
C positive electrode material.
(4) prepare lithium titanate precursor peroxide titanium compound：
Step (1) gained richness titanium is leached white to presenting in 60 DEG C of heating stirrings after addition 12.5wt% weak aqua ammonia in filter residue
Color suspension, continue dropping 12.5wt% weak aqua ammonia to adjust pH value is 7, then under vigorous stirring, leaches filter by every gram of rich titanium
Slag adds 5mlH2O2, supplement ammoniacal liquor and stablize pH value to 7, add dense H2SO4It is in orange-yellow to suspension, continue reaction 1h, filter
Obtain leachate, 100 DEG C of heating of leachate are evaporated, obtain faint yellow xerogel, as lithium titanate precursor peroxide titanizing
Compound.Crossing filter residue is SILICA FUME.
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined 4h in 500 DEG C, obtains TiO2Powder；By 6gTiO2With
2.22gLi2CO3Mix, 810 DEG C of calcining 7h of in the air, after along with the furnace cooling, obtain final product lithium titanate Li4Ti5O12Negative material powder
Body.
Referring to Fig. 6 a and Fig. 6 b, the respectively LiFePO of the present embodiment gained4And Li4Ti5O12SEM figure.
Embodiment 6
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 28%, hydrochloric acid with
The mass ratio of vanadium extraction waste is 2.65,75 DEG C of extraction temperature, and extraction time is 2.5h；After the completion of leaching, gained slurry is cooled to
Room temperature, is filtrated to get Fu Tie and leaches filtrate and rich titanium leaching filter residue.
(2) prepare ferric lithium phosphate precursor ferric phosphate：
HCl free in step (1) gained leachate is carried out steaming acid recovery process, obtains concentrating leachate, be configured to
The rich iron leachate of 0.425 molar concentration.It is 0.85 by Fe/P mol ratio, by phosphoric acid H3PO4Add in rich iron leachate, 35 DEG C
After heating stirring 0.9h, add the oxydol H of 0.54 times of ferrous iron mole2O2Stirring reaction 25min, ammonification water adjusts molten
Liquid system pH value is 3.5, reacts 1.5h further, gained precipitation filters and washing and drying, that is, obtain LiFePO4 forerunner
Body ferric phosphate FePO4Powder.
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
2.265g ferric phosphate FePO by gained in step (2)4With 0.555gLi2CO3And 1.285g rock sugar mixes,
Under inert gas shielding in atmosphere furnace, 770 DEG C of calcining 12h, take out after cooling, that is, obtain LiFePO4/ C positive electrode material.
(4) prepare lithium titanate precursor peroxide titanium compound：
Step (1) gained richness titanium is leached white to presenting in 35 DEG C of heating stirrings after addition 12.5wt% weak aqua ammonia in filter residue
Color suspension, continue dropping 12.5wt% weak aqua ammonia to adjust pH value is 4.5, then under vigorous stirring, leaches by every gram of rich titanium
Filter residue adds 2.5mlH2O2, supplement ammoniacal liquor and stablize pH value to 4.5, add dense H2SO4It is in orange-yellow to suspension, continue reaction
1h, is filtrated to get leachate, 100 DEG C of heating of leachate is evaporated, obtains faint yellow xerogel, as lithium titanate precursor mistake
Oxygen titanium compound.Crossing filter residue is SILICA FUME.
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined 4h in 500 DEG C, obtains TiO2Powder；By 6gTiO2With
2.22gLi2CO3Mix, 780 DEG C of calcining 9h of in the air, after along with the furnace cooling, obtain final product lithium titanate Li4Ti5O12Negative material powder
Body.
Referring to Fig. 7 a and Fig. 7 b, the respectively LiFePO of the present embodiment gained4And Li4Ti5O12SEM figure.
Embodiment 7
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 19%, hydrochloric acid with
The mass ratio of vanadium extraction waste is 2.35,85 DEG C of extraction temperature, and extraction time is 3.5h；After the completion of leaching, gained slurry is cooled to
Room temperature, is filtrated to get Fu Tie and leaches filtrate and rich titanium leaching filter residue.
(2) prepare ferric lithium phosphate precursor ferric phosphate：
HCl free in step (1) gained leachate is carried out steaming acid recovery process, obtains concentrating leachate, be configured to
The rich iron leachate of 0.65 molar concentration.It is 0.95 by Fe/P mol ratio, by phosphoric acid H3PO4Add in rich iron leachate, 45 DEG C add
After thermal agitation 0.5h, add the oxydol H of 0.46 times of ferrous iron mole2O2Stirring reaction 20min, ammonification water adjusts solution
System pH is 4, reacts 2.5h further, gained precipitation filters and washing and drying, that is, obtain ferric lithium phosphate precursor phosphoric acid
Iron FePO4Powder.
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
2.265g ferric phosphate FePO by gained in step (2)4、0.555gLi2CO3And 3.369g agar powder mixes,
Under inert gas shielding in atmosphere furnace, 780 DEG C of calcining 13h, take out after cooling, that is, obtain LiFePO4/ C positive electrode material.
(4) prepare lithium titanate precursor peroxide titanium compound：
Step (1) gained richness titanium is leached white to presenting in 45 DEG C of heating stirrings after addition 12.5wt% weak aqua ammonia in filter residue
Color suspension, continue dropping 12.5wt% weak aqua ammonia to adjust pH value is 5.5, then under vigorous stirring, leaches by every gram of rich titanium
Filter residue adds 3.5mlH2O2, supplement ammoniacal liquor and stablize pH value to 5.5, add dense H2SO4It is in orange-yellow to suspension, continue reaction
1h, is filtrated to get leachate, 100 DEG C of heating of leachate is evaporated, obtains faint yellow xerogel, as lithium titanate precursor mistake
Oxygen titanium compound.Crossing filter residue is SILICA FUME.
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined 4h in 500 DEG C, obtains TiO2Powder；By 6gTiO2With
2.22gLi2CO3Mix, 790 DEG C of calcining 6.5h of in the air, after along with the furnace cooling, obtain final product lithium titanate Li4Ti5O12Negative material
Powder.
Referring to Fig. 8 a and Fig. 8 b, the respectively LiFePO of the present embodiment gained4And Li4Ti5O12SEM figure.
Embodiment 8
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 23%, hydrochloric acid with
The mass ratio of vanadium extraction waste is 2.725,95 DEG C of extraction temperature, and extraction time is 4.5h；After the completion of leaching, gained slurry is cooled down
To room temperature, it is filtrated to get Fu Tie and leaches filtrate and rich titanium leaching filter residue.
(2) prepare ferric lithium phosphate precursor ferric phosphate：
HCl free in step (1) gained leachate is carried out steaming acid recovery process, obtains concentrating leachate, be configured to
The rich iron leachate of 0.375 molar concentration.It is 0.925 by Fe/P mol ratio, by phosphoric acid H3PO4Add in rich iron leachate, 55 DEG C
After heating stirring 0.6h, add the oxydol H of 0.55 times of ferrous iron mole2O2Stirring reaction 30min, ammonification water adjusts molten
Liquid system pH value is 3, reacts 3h further, gained precipitation filters and washing and drying, that is, obtain ferric lithium phosphate precursor phosphorus
Sour iron FePO4Powder.
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
2.265g ferric phosphate FePO by gained in step (2)4With 0.555gLi2CO3And 5.485g gelatin mixes,
Under inert gas shielding in atmosphere furnace, 740 DEG C of calcining 14h, take out after cooling, that is, obtain LiFePO4/ C positive electrode material.
(4) prepare lithium titanate precursor peroxide titanium compound：
Step (1) gained richness titanium is leached white to presenting in 55 DEG C of heating stirrings after addition 12.5wt% weak aqua ammonia in filter residue
Color suspension, continue dropping 12.5wt% weak aqua ammonia to adjust pH value is 6.5, then under vigorous stirring, leaches by every gram of rich titanium
Filter residue adds 4.5mlH2O2, supplement ammoniacal liquor and stablize pH value to 6.5, add dense H2SO4It is in orange-yellow to suspension, continue reaction
1h, is filtrated to get leachate, 100 DEG C of heating of leachate is evaporated, obtains faint yellow xerogel, as lithium titanate precursor mistake
Oxygen titanium compound.Crossing filter residue is SILICA FUME.
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined 4h in 500 DEG C, obtains TiO2Powder；By 6gTiO2With
2.22gLi2CO3Mix, 820 DEG C of calcining 7.5h of in the air, after along with the furnace cooling, obtain final product lithium titanate Li4Ti5O12Negative material
Powder.
Referring to Fig. 9 a and Fig. 9 b, the respectively LiFePO of the present embodiment gained4And Li4Ti5O12SEM figure.
Embodiment 9
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 31%, hydrochloric acid with
The mass ratio of vanadium extraction waste is 2.0,105 DEG C of extraction temperature, and extraction time is 3h；After the completion of leaching, gained slurry is cooled to room
Temperature, is filtrated to get Fu Tie and leaches filtrate and rich titanium leaching filter residue.
(2) prepare ferric lithium phosphate precursor ferric phosphate：
HCl free in step (1) gained leachate is carried out steaming acid recovery process, obtains concentrating leachate, be configured to
The rich iron leachate of 0.75 molar concentration.It is 0.97 by Fe/P mol ratio, by phosphoric acid H3PO4Add in rich iron leachate, 65 DEG C add
After thermal agitation 1h, add the oxydol H of 0.47 times of ferrous iron mole2O2Stirring reaction 10min, ammonification water adjusts solution body
Be pH value be 4, further react 5h, gained precipitation filter and washing and drying, that is, obtain ferric lithium phosphate precursor ferric phosphate
FePO4Powder.
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
2.265g ferric phosphate FePO by gained in step (2)4With 0.555gLi2CO3And the mixing of 1.043g citric acid is all
Even, under inert gas shielding in atmosphere furnace, 810 DEG C of calcining 8h, take out after cooling, that is, obtain LiFePO4/ C positive electrode material.
(4) prepare lithium titanate precursor peroxide titanium compound：
Step (1) gained richness titanium is leached white to presenting in 65 DEG C of heating stirrings after addition 12.5wt% weak aqua ammonia in filter residue
Color suspension, continue dropping 12.5wt% weak aqua ammonia to adjust pH value is 7.5, then under vigorous stirring, leaches by every gram of rich titanium
Filter residue adds 5.5mlH2O2, supplement ammoniacal liquor and stablize pH value to 7.5, add dense H2SO4It is in orange-yellow to suspension, continue reaction
1h, is filtrated to get leachate, 100 DEG C of heating of leachate is evaporated, obtains faint yellow xerogel, as lithium titanate precursor mistake
Oxygen titanium compound.Crossing filter residue is SILICA FUME.
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined 4h in 500 DEG C, obtains TiO2Powder；By 6gTiO2With
2.22gLi2CO3Mix, 770 DEG C of calcining 8.5h of in the air, after along with the furnace cooling, obtain final product lithium titanate Li4Ti5O12Negative material
Powder.
Referring to Figure 10 a and Figure 10 b, the respectively LiFePO of the present embodiment gained4And Li4Ti5O12SEM figure.
Embodiment 10
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 15%, hydrochloric acid with
The mass ratio of vanadium extraction waste is 2.125,70 DEG C of extraction temperature, and extraction time is 2h；After the completion of leaching, gained slurry is cooled to
Room temperature, is filtrated to get Fu Tie and leaches filtrate and rich titanium leaching filter residue.
(2) prepare ferric lithium phosphate precursor ferric phosphate：
HCl free in step (1) gained leachate is carried out steaming acid recovery process, obtains concentrating leachate, be configured to
The rich iron leachate of 0.265 molar concentration.It is 0.75 by Fe/P mol ratio, by phosphoric acid H3PO4Add in rich iron leachate, 30 DEG C
After heating stirring 0.5h, add the oxydol H of 0.45 times of ferrous iron mole2O2Stirring reaction 10min, ammonification water adjusts molten
Liquid system pH value is 2, reacts 1h further, gained precipitation filters and washing and drying, that is, obtain ferric lithium phosphate precursor phosphoric acid
Iron FePO4Powder.
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
2.265g ferric phosphate FePO by gained in step (2)4With 0.555gLi2CO3And 1.184g agar powder, 2.241g
Gelatin, 0.361g citric acid and 0.642g rock sugar mix, and under inert gas shielding in atmosphere furnace, 700 DEG C of calcining 8h, treat
Take out after cooling, that is, obtain LiFePO4/ C positive electrode material.
(4) prepare lithium titanate precursor peroxide titanium compound：
Step (1) gained richness titanium is leached white to presenting in 70 DEG C of heating stirrings after addition 12.5wt% weak aqua ammonia in filter residue
Color suspension, continue dropping 12.5wt% weak aqua ammonia to adjust pH value is 4, then under vigorous stirring, leaches filter by every gram of rich titanium
Slag adds 2mlH2O2, supplement ammoniacal liquor and stablize pH value to 4, add dense H2SO4It is in orange-yellow to suspension, continue reaction 1h, filter
Obtain leachate, 100 DEG C of heating of leachate are evaporated, obtain faint yellow xerogel, as lithium titanate precursor peroxide titanizing
Compound.Crossing filter residue is SILICA FUME.
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined 4h in 500 DEG C, obtains TiO2Powder；By 6gTiO2With
2.22gLi2CO3Mix, 830 DEG C of calcining 9.5h of in the air, after along with the furnace cooling, obtain final product lithium titanate Li4Ti5O12Negative material
Powder.
Referring to Figure 11 a and Figure 11 b, the respectively LiFePO of the present embodiment gained4And Li4Ti5O12SEM figure.
Finally it should be noted that：Although the present invention and its advantage have below been described in detail it should be appreciated that not
Beyond can carry out in the case of the spirit and scope of the present invention that are defined by the claims appended hereto various changes, replacement and
Conversion.And, the scope of the present invention is not limited only to process described by specification, equipment, means, the concrete reality of method and steps
Apply example.One of ordinary skilled in the art will readily appreciate that from the disclosure, can be used according to the present invention and hold
The row function essentially identical to corresponding embodiment described herein or obtain result, the existing and future essentially identical with it
Process to be developed, equipment, means, method or step.Therefore, appended claim is directed at bag in the range of them
Include such process, equipment, means, method or step.
Claims (4)
1. a kind of vanadium extraction waste prepare electrode material of lithium battery LiFePO4 and lithium titanate method it is characterised in that include with
Lower step：
(1) ferrotitanium separates：
After vanadium extraction waste Mechanical Crushing, with salt Ore Leaching vanadium extraction waste, be filtrated to get after the completion of leaching Fu Tie leach filtrate and
Rich titanium leaches filter residue；
In described step (1)：Leach vanadium extraction waste, hydrochloric acid and vanadium extraction waste with the hydrochloric acid of mass concentration 15-35% at ambient pressure
Mass ratio be 1.5-3.0,70-110 DEG C of extraction temperature, extraction time be 1-5h；After the completion of leaching, gained slurry is cooled to
Room temperature, then filtered；
(2) prepare ferric lithium phosphate precursor：
Leach free HCl in filtrate to step (1) gained richness iron to carry out steaming acid recovery process, obtain concentrating leachate, be configured to
Rich iron leachate；By precipitating reagent phosphoric acid H3PO4Add in rich iron leachate, add oxidant hydrogen peroxide H2O2Stirring reaction, plus
Ammoniacal liquor adjusts solution system pH value, reacts further, and gained precipitation filters and washing and drying, that is, obtain ferric lithium phosphate precursor
Ferric phosphate FePO4Powder；
In described step (2)：Concentrate the rich iron leachate that leachate is configured to 0.2-0.8 molar concentration；Ammonification water adjusts solution
System pH is 2-4；
After adding phosphoric acid, after 30-70 DEG C of heating stirring 0.5-1h, add oxidant stirring reaction 5-30min；Ammonification water is follow-up
Continuous reaction 1-5h；
Wherein, in solution, divalence Fe mole and the addition of precipitating reagent are Fe/P mol ratio 0.75-1：1, the addition of oxidant
Measure 0.45-0.55 times for divalence Fe mole in solution；
(3) prepare LiFePO4 LiFePO4Positive electrode material of lithium secondary cell：
Ferric phosphate FePO by gained in step (2)4Presoma and Li2CO3And organic carbon source mixes, lazy in atmosphere furnace
Property gas shield under calcine, take out after cooling, that is, obtain LiFePO4/ C positive electrode material；
In described step (3)：Described ferric phosphate FePO4Presoma and Li2CO3And the mol ratio 2 of organic carbon source:1：(0.5～1)；
In described atmosphere furnace, the temperature of calcining is 700-800 DEG C, and calcination time is 8-15h；
(4) prepare lithium titanate precursor：
Filter residue is leached to gained richness titanium in step (1) and adds NH3·H2O, heats and stirs, add H2O2, adding H2O2Cross
In journey, constantly dropping ammoniacal liquor adjusts pH value, is subsequently adding dense H2SO4Continue reaction, filter out filtrate, by filtrate heating response, face
Discoloration shallow to milky, be evaporated and obtain faint yellow xerogel, as lithium titanate precursor peroxide titanium compound；It is micro- for crossing filter residue
Silica flour；
In described step (4)：
In 30-70 DEG C of heating stirring to assuming white suspension after adding 12.5wt% weak aqua ammonia, continue dropping 12.5wt% dilute
It is 4-8 that ammoniacal liquor adjusts pH value, then under agitation, leaches filter residue by every gram of rich titanium and adds 2-6mlH2O2, supplement ammoniacal liquor and stablize pH
It is worth to setting value, add dense H2SO4It is in orange-yellow to suspension, continue reaction 0.5-1.5h, be filtrated to get leachate, will leach
90-110 DEG C of heating of liquid is evaporated, and obtains peroxide titanium compound；
(5) prepare lithium titanate Li4Ti5O12Lithium secondary battery cathode material：
Step (4) gained peroxide titanium compound is calcined, obtains TiO2Powder；By TiO2Powder and Li2CO3Mix, air
Middle calcining, obtains final product lithium titanate Li after along with the furnace cooling4Ti5O12Negative electrode material powder；
The calcining heat of described peroxide titanium compound is 400-600 DEG C of calcining 3-5h；Described TiO2Powder and Li2CO3By Li:Ti
Mol ratio 4:5 mix, and described in the air calcining heat is 750-850 DEG C, and calcination time is 5-10h.
2. method according to claim 1 is it is characterised in that described LiFePO4 LiFePO4Positive electrode material of lithium secondary cell
Organic carbon source used is selected from least one in glucose, starch, sucrose, agar powder, gelatin, citric acid and rock sugar.
3. battery electrode material LiFePO4 is it is characterised in that prepare according to the method described in claim 1 or 2.
4. battery electrode material lithium titanate is it is characterised in that prepare according to the method described in claim 1 or 2.
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| CN105140504B (en) * | 2015-08-11 | 2018-02-02 | 东北大学 | A kind of method that electrode material of lithium battery is prepared using vanadium extraction waste |
| CN105703031B (en) * | 2016-03-21 | 2018-10-23 | 上海交通大学 | The method for preparing doping type catalysis material using negative electrode of lithium titanate battery waste material |
| CN106532172B (en) * | 2016-12-23 | 2019-05-21 | 江西合纵锂业科技有限公司 | A method of the Selectively leaching lithium from failure lithium iron phosphate battery positive material |
| CN106834749B (en) * | 2017-02-09 | 2019-01-29 | 东北大学 | The method of Vanadium Concentrationin from v-bearing steel slag |
| CN109250696B (en) * | 2017-07-12 | 2020-05-08 | 深圳佳彬科技有限公司 | Method for recovering nano iron phosphate from lithium iron phosphate battery |
| SE543505C2 (en) * | 2019-04-15 | 2021-03-09 | Northvolt Ab | Process for the recovery of cathode materials in the recycling of lithium ion batteries |
| CN113851618B (en) * | 2021-08-10 | 2023-06-23 | 桂林理工大学 | Method for preparing high-performance ferric phosphate/graphene composite anode material by utilizing hydrochloric acid leaching solution of iron vitriol slag and application of high-performance ferric phosphate/graphene composite anode material |
| CN115367725B (en) * | 2022-08-29 | 2024-05-10 | 广东邦普循环科技有限公司 | Doped lithium iron phosphate and preparation method and application thereof |
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