CN104805299A - 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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- CN104805299A CN104805299A CN201510176302.9A CN201510176302A CN104805299A CN 104805299 A CN104805299 A CN 104805299A CN 201510176302 A CN201510176302 A CN 201510176302A CN 104805299 A CN104805299 A CN 104805299A
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- iron
- lithium
- rich
- gained
- vanadium extraction
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Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 109
- 238000000605 extraction Methods 0.000 title claims abstract description 86
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 63
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000007772 electrode material Substances 0.000 title claims abstract description 13
- 239000002893 slag Substances 0.000 title abstract description 7
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 title abstract 5
- 229910052493 LiFePO4 Inorganic materials 0.000 title abstract 4
- 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 87
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 62
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000010936 titanium Substances 0.000 claims abstract description 46
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 43
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 claims abstract description 35
- 235000011114 ammonium hydroxide Nutrition 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
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- -1 titanium peroxide compound Chemical class 0.000 claims abstract description 20
- 239000010405 anode material Substances 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 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
- 239000002699 waste material Substances 0.000 claims description 57
- 238000001354 calcination Methods 0.000 claims description 42
- 238000002386 leaching Methods 0.000 claims description 41
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 40
- 229910010710 LiFePO Inorganic materials 0.000 claims description 35
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 26
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 24
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000004062 sedimentation Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 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
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 12
- 229910021487 silica fume Inorganic materials 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000010025 steaming Methods 0.000 claims description 12
- 238000001556 precipitation Methods 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
- 239000008103 glucose Substances 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
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 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 4
- 239000008272 agar Substances 0.000 claims description 4
- 239000003795 chemical substances by application 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
- 239000011435 rock Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- IAHBIMWHYUOIOH-UHFFFAOYSA-N vanadium hydrochloride Chemical compound Cl.[V] IAHBIMWHYUOIOH-UHFFFAOYSA-N 0.000 claims description 3
- 241000237502 Ostreidae Species 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 235000020636 oyster Nutrition 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 2
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 2
- 229910000901 LiFePO4/C Inorganic materials 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004568 cement Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005516 engineering process Methods 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
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 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
- 239000000126 substance 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
- 239000005955 Ferric phosphate Substances 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003245 coal 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
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000012530 fluid Substances 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
- 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
- 238000004064 recycling 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
- 150000003608 titanium Chemical class 0.000 description 1
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 the presoma method of lithium ion battery electrode material, be specifically related to the method that vanadium extraction waste prepares electrode material of lithium battery iron lithium phosphate and lithium titanate.
Background technology
In recent years, the iron lithium phosphate of olivine structural is because having high (the 170mAh 〃 g of theoretical specific capacity
-1), good cycle, Heat stability is good, cheap, advantages of environment protection, become 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 safety performance (Li because of it
4ti
5o
12: Li/Li relatively
tenreduction potential be 1.5V, metallic lithium can be avoided to separate out), be considered to a kind of well high power lithium ion cell and asymmetric hybrid battery negative material.The quality of lithium titanate and iron lithium phosphate performance is decided by the quality of its presoma to a great extent, and the presoma preparing iron lithium phosphate and lithium titanate is at present mostly high-purity molysite or titanium salt.These raw material major parts are obtained through a series of removal of impurities operation by ore, and when preparing iron lithium phosphate and lithium titanate with these high pure raw materials, need to add some doped elements (as Mg, Mn, Nb, Cr etc.) useful to its chemical property, these doped elements just exist mostly in natural mineral, thus causing flow process to repeat, cost increases greatly.Therefore, the presoma directly utilizing mineral (or waste material) to prepare 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, reserves occupy third place in the world after being positioned at South Africa and Russia, are mainly distributed in Sichuan, area, Chengde.Calcium in v-bearing steel slag, iron level are high, and content of vanadium is low, and occurrence patterns is complicated, and recycle difficulty very large, from slag, vanadium extraction remains a global difficult problem at present.Except continuing vanadium extraction, at present, the recycling containing vanadium solid waste also has two large classes: as functionality ceramic raw material and cement raw material.The former as above-mentioned take vanadium titano-magnetite as the main raw material of the vanadium extraction waste of raw material or ornamental pottery-black ceramic tinting material functional as preparation, the latter is that raw material vanadium-extracted residues is used as cement mixture with stone coal mine.Although above Application way is whole utilization, in fact all with only the effect of a part of composition in waste, added value is not high, and particularly Ti resource utilization is very low.And arbitrarily pile and abandon, the diffusion potential that dissociates of the poisonous ion of the heavy metal such as Qi Zhongfan, chromium must cause environment and directly pollute and disaster hidden danger.
Summary of the invention
Provide hereinafter about brief overview of the present invention, to provide about the basic comprehension in some of the present invention.Should be appreciated that this general introduction is not summarize about exhaustive of the present invention.It is not that intention determines key of the present invention or integral part, and nor is it intended to limit the scope of the present invention.Its object is only provide some concept in simplified form, in this, as the preorder in greater detail discussed after a while.
The object of the embodiment of the present invention is the defect for above-mentioned prior art, provides a kind of environmentally friendly, reclamation of solid wastes and the high vanadium extraction waste of added value utilization ratio to prepare the method for electrode material of lithium battery iron lithium phosphate and lithium titanate.
To achieve these goals, the technical scheme that the present invention takes is:
A method for vanadium extraction waste electrode material of lithium battery iron lithium phosphate and lithium titanate, comprises the following steps:
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, with Leaching in Hydrochloric Acid vanadium extraction waste, leach rear filtration and obtained Fu Tie leaching filtrate and rich titanium leaching filter residue;
(2) ferric lithium phosphate precursor is prepared:
Free HCl in filtrate is leached to the rich iron of step (1) gained and carries out steaming acid recovery process, obtain concentrated leach liquor, be mixed with rich iron leach liquor; By precipitation agent phosphoric acid H
3pO
4add in rich iron leach liquor, then add oxidant hydrogen peroxide H
2o
2stirring reaction, adds ammoniacal liquor regulator solution system pH, reacts further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor-tertiary iron phosphate FePO
4powder;
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the tertiary iron phosphate FePO of gained in step (2)
4presoma and Li
2cO
3and organic carbon source mixes, calcine under protection of inert gas in atmosphere furnace, take out after cooling, namely obtain LiFePO
4/ C positive electrode material;
(4) lithium titanate precursor is prepared:
Filter residue is leached to the rich titanium of gained in step (1) and adds NH
3h
2o, heats and stirs, then adding H
2o
2, adding H
2o
2constantly drip ammoniacal liquor adjust ph in process, then add dense H
2sO
4continue reaction, filter out filtrate, by filtrate reacting by heating, lighter is to oyster white, and evaporate to dryness obtains faint yellow xerogel, is lithium titanate precursor-peroxide titanium compound; Crossing filter residue is SILICA FUME;
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
Step (4) gained peroxide titanium compound is calcined, obtains TiO
2powder; By TiO
2powder and Li
2cO
3mix, calcine in air, after furnace cooling, namely obtain lithium titanate Li
4ti
5o
12negative electrode material powder.
In described step (1): leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 15-35%, the mass ratio of hydrochloric acid and vanadium extraction waste is 1.5-3.0, extraction temperature 70-110 DEG C, and extraction time is 1-5h; After leaching completes, gained slurry is cooled to room temperature, then filters.
In described step (2): concentrated leach liquor is mixed with the rich iron leach liquor of 0.2-0.8 volumetric molar concentration; Adding ammoniacal liquor regulator solution system pH is 2-4;
After adding phosphoric acid, after 30-70 DEG C of heated and stirred 0.5-1h, then add oxygenant stirring reaction 5-30min; Add the follow-up continuous reaction 1-5h of ammoniacal liquor;
Wherein, in solution, the add-on of divalence Fe molar weight and precipitation agent is Fe/P mol ratio 0.75-1:1, and the add-on of oxygenant is 0.45-0.55 times of divalence Fe molar weight in solution.
In described step (3): in described step (3): described tertiary iron phosphate FePO
4presoma and Li
2cO
3and mol ratio 2:1:(0.5 ~ 1 of organic carbon source);
The temperature of calcining in described atmosphere furnace is 700-800 DEG C, and calcination time is 8-15h.
In described step (4):
After adding 12.5wt% weak ammonia 30-70 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 4-8, then under vigorous stirring, leaches filter residue add 2-6mlH by every gram of rich titanium
2o
2, supplementary ammoniacal liquor stablizes pH value to set(ting)value, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 0.5-1.5h, filter and obtain leach liquor, by leach liquor 90-110 DEG C of heating evaporate to dryness, obtain peroxide titanium compound.
In described step (5):
The calcining temperature of described peroxide titanium compound is 400-600 DEG C of calcining 3-5h; Described TiO
2powder and Li
2cO
3mix by Li:Ti mol ratio 4:5, in described air, calcining temperature is 750-850 DEG C, and calcination time is 5-10h.
Described iron lithium phosphate LiFePO
4anode material for lithium secondary battery organic carbon source used is selected from least one in glucose, starch, sucrose, agar powder, gelatin, citric acid and rock sugar.
The present invention also provides a kind of electrode material of lithium battery iron lithium phosphate and lithium titanate, prepares according to above-mentioned method.
Compared with prior art, the invention has the beneficial effects as follows:
It is raw material that the present invention make use of this industrial bulk solid waste of vanadium extraction waste well, synthesize the presoma of the electrode materials of two kinds of lithium celies simultaneously, the i.e. presoma of LiFePO 4 of anode material---ferrous acid lithium, and the presoma-titanium dioxide of lithium titanate of negative pole material, prepare iron lithium phosphate LiFePO further
4positive electrode material and lithium titanate Li
4ti
5o
12negative material.Other micro-metalss (aluminium, magnesium, manganese etc.) in preparation process outside deironing in vanadium extraction waste, titanium are evenly distributed in presoma crystal grain, without the need to adulterating when making synthesis subsequent electrode material, these doped elements can improve the chemical property of iron lithium phosphate and lithium titanate greatly again.Therefore; the present invention is particularly suitable for as the production of lithium ion battery anode material lithium iron phosphate and lithium titanate of negative pole material provides source of iron and the titanium source of high-quality cheapness; achieve the efficient of each element of vanadium extraction waste and sustainable use fully; avoid environmental pollution; added value utilization ratio is high, for large-scale production brings huge economic benefit and environmental protection social benefit.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the electrode materials-LiFePO preparing lithium secondary battery from vanadium extraction waste
4and Li
4ti
5o
12process flow sheet;
Fig. 2 a is LiFePO in embodiment 1
4sEM (Scanning Electron Microscope, scanning electronic microscope) figure;
Fig. 2 b is Li in embodiment 1
4ti
5o
12sEM figure;
Fig. 3 a is LiFePO in embodiment 2
4sEM figure;
Fig. 3 b is Li in embodiment 2
4ti
5o
12sEM figure;
Fig. 4 a is LiFePO in embodiment 3
4sEM figure;
Fig. 4 b is Li in embodiment 3
4ti
5o
12sEM figure;
Fig. 5 a is LiFePO in embodiment 4
4sEM figure;
Fig. 5 b is Li in embodiment 4
4ti
5o
12sEM figure;
Fig. 6 a is LiFePO in embodiment 5
4sEM figure;
Fig. 6 b is Li in embodiment 5
4ti
5o
12sEM figure;
Fig. 7 a is LiFePO in embodiment 6
4sEM figure;
Fig. 7 b is Li in embodiment 6
4ti
5o
12sEM figure;
Fig. 8 a is LiFePO in embodiment 7
4sEM figure;
Fig. 8 b is Li in embodiment 7
4ti
5o
12sEM figure;
Fig. 9 a is LiFePO in embodiment 8
4sEM figure;
Fig. 9 b is Li in embodiment 8
4ti
5o
12sEM figure;
Figure 10 a is LiFePO in embodiment 9
4sEM figure;
Figure 10 b is Li in embodiment 9
4ti
5o
12sEM figure;
Figure 11 a is LiFePO in embodiment 10
4sEM figure;
Figure 11 b is Li in embodiment 10
4ti
5o
12sEM figure.
Embodiment
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.The element described in an accompanying drawing of the present invention or a kind of embodiment and feature can combine with the element shown in one or more other accompanying drawing or embodiment and feature.It should be noted that for purposes of clarity, accompanying drawing and eliminate expression and the description of unrelated to the invention, parts known to persons of ordinary skill in the art and process in illustrating.Based on the embodiment in the present invention, those of ordinary skill in the art, not paying the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
See Fig. 1, a kind of method utilizing vanadium extraction waste to prepare iron lithium phosphate and lithium titanate.Comprise the following steps:
(1) ferrotitanium is separated: by vanadium extraction waste Mechanical Crushing, with Leaching in Hydrochloric Acid vanadium extraction waste, and solid-liquid separation is filtered and obtained rich iron leach liquor and rich titanium leached mud;
(2) preparation of ferric lithium phosphate precursor---tertiary iron phosphate: take leach liquor as raw material, adopts H
3pO
4tertiary iron phosphate is prepared in selective precipitation.By the H of certain mol proportion example
3pO
4solution joins in fluid, violent stirring, adds a certain amount of hydrogen peroxide, makes Fe (II) all be oxidized to Fe (III), finally uses ammoniacal liquor adjust ph, isothermal reaction, gained sedimentation and filtration washing and drying, namely obtains ferric phosphate powder body.
(3) preparation of iron lithium phosphate: take tertiary iron phosphate as raw material, adopts carbothermic method synthesis LiFePO
4/ C anode material for lithium secondary battery.Stoichiometrically take Li
2cO
3, presoma and organic carbon source, mix, calcine under protection of inert gas in atmosphere furnace, take out after cooling, namely obtain containing LiFePO metal-doped on a small quantity
4/ C positive electrode material.
(4) at H
2o
2-NH
3〃 H
2o-H
2sO
4system, carries out Selectively leaching to the titanium in leached mud, obtains titanium peroxide compound, preparation TiO
2and Li
4ti
5o
12negative material.
The each valuable element of whole utilization vanadium extraction waste of the present invention, synthesis lithium battery material LiFePO
4and Li
4ti
5o
12deng high value added product, achieve efficiency utilization and the environment protection of vanadium extraction waste.
Ferric lithium phosphate precursor of the present invention-tertiary iron phosphate FePO
4raw material be vanadium extraction waste iron leach liquor.Lithium titanate precursor-peroxide titanium compound is in sour environment, uses H
2o
2-NH
3〃 H
2o system carries out to the rich titanium titanium leached in filter residue that Selectively leaching obtains.
The present invention with unmanageable repeatedly water logging vanadium extraction waste for raw material, use selective precipitation technology to prepare lithium ionic cell cathode material lithium titanate and LiFePO 4 of anode material presoma, and then low cost prepare this two kinds of lithium ion battery positive and negative electrode material-LiFePO
4and Li
4ti
5o
12, 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 is separated:
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 15%, the mass ratio of hydrochloric acid and vanadium extraction waste is 2.125, extraction temperature 70 DEG C, and extraction time is 2h; After leaching completes, gained slurry is cooled to room temperature, filters and obtain Fu Tie leaching filtrate and rich titanium leaching filter residue.
(2) ferric lithium phosphate precursor is prepared---tertiary iron phosphate:
Steaming acid recovery process is carried out to HCl free in step (1) gained leach liquor, obtains concentrated leach liquor, be mixed with the rich iron leach liquor of 0.265 volumetric molar concentration.Be 0.75 by Fe/P mol ratio, by phosphoric acid H
3pO
4add in rich iron leach liquor, after 30 DEG C of heated and stirred 0.5h, then add the oxydol H of 0.45 times of ferrous iron molar weight
2o
2stirring reaction 10min, adding ammoniacal liquor regulator solution system pH is 2, reacts 1h further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor---tertiary iron phosphate FePO
4powder.
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the 2.265g tertiary iron phosphate FePO of gained in step (2)
4with 0.555gLi
2cO
3and 1.353g glucose mixes, in atmosphere furnace, 700 DEG C of calcining 8h under protection of inert gas, take out after cooling, namely obtain LiFePO
4/ C positive electrode material.
(4) lithium titanate precursor-peroxide titanium compound is prepared:
To the rich titanium of step (1) gained leach add 12.5wt% weak ammonia in filter residue after 30 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 4, then under vigorous stirring, leach filter residue by every gram of rich titanium and add 2mlH
2o
2, supplementary ammoniacal liquor stablizes pH value to 4, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 1h, filter and obtain leach liquor, by leach liquor 100 DEG C heating evaporate to dryness, obtain faint yellow xerogel, be lithium titanate precursor-peroxide titanium compound.Crossing filter residue is SILICA FUME.
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
By step (4) gained peroxide titanium compound in 500 DEG C of calcining 4h, obtain TiO
2powder; By 6gTiO
2with 2.22gLi
2cO
3mix, in air, 750 DEG C of calcining 5h, namely obtain lithium titanate Li after furnace cooling
4ti
5o
12negative electrode material powder.
See Fig. 2 a and Fig. 2 b, be respectively the LiFePO of the present embodiment gained
4and Li
4ti
5o
12sEM figure.
Embodiment 2
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 20%, the mass ratio of hydrochloric acid and vanadium extraction waste is 1.75, extraction temperature 90 DEG C, and extraction time is 5h; After leaching completes, gained slurry is cooled to room temperature, filters and obtain Fu Tie leaching filtrate and rich titanium leaching filter residue.
(2) ferric lithium phosphate precursor-tertiary iron phosphate is prepared:
Steaming acid recovery process is carried out to HCl free in step (1) gained leach liquor, obtains concentrated leach liquor, be mixed with the rich iron leach liquor of 0.528 volumetric molar concentration.Be 0.87 by Fe/P mol ratio, by phosphoric acid H
3pO
4add in rich iron leach liquor, after 70 DEG C of heated and stirred 1h, then add the oxydol H of 0.55 times of ferrous iron molar weight
2o
2stirring reaction 5min, adding ammoniacal liquor regulator solution system pH is 4, reacts 5h further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor-tertiary iron phosphate FePO
4powder.
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the 2.265g tertiary iron phosphate FePO of gained in step (2)
4with 0.555gLi
2cO
3and 0.618g starch mixes, in atmosphere furnace, 800 DEG C of calcining 15h under protection of inert gas, take out after cooling, namely obtain LiFePO
4/ C positive electrode material.
(4) lithium titanate precursor-peroxide titanium compound is prepared:
To the rich titanium of step (1) gained leach add 12.5wt% weak ammonia in filter residue after 40 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 8, then under vigorous stirring, leach filter residue by every gram of rich titanium and add 6mlH
2o
2, supplementary ammoniacal liquor stablizes pH value to 8, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 0.5h, filter and obtain leach liquor, by leach liquor 90 DEG C heating evaporate to dryness, obtain faint yellow xerogel, be lithium titanate precursor-peroxide titanium compound.Crossing filter residue is SILICA FUME.
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
By step (4) gained peroxide titanium compound in 400 DEG C of calcining 6h, obtain TiO
2powder; By 6gTiO
2with 2.22gLi
2cO
3mix, in air, 850 DEG C of calcining 10h, namely obtain lithium titanate Li after furnace cooling
4ti
5o
12negative electrode material powder.
See Fig. 3 a and Fig. 3 b, be respectively the LiFePO of the present embodiment gained
4and Li
4ti
5o
12sEM figure.
Embodiment 3
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 35%, the mass ratio of hydrochloric acid and vanadium extraction waste is 2.5, extraction temperature 110 DEG C, and extraction time is 1h; After leaching completes, gained slurry is cooled to room temperature, filters and obtain Fu Tie leaching filtrate and rich titanium leaching filter residue.
(2) ferric lithium phosphate precursor-tertiary iron phosphate is prepared:
Steaming acid recovery process is carried out to HCl free in step (1) gained leach liquor, obtains concentrated leach liquor, be mixed with the rich iron leach liquor of 0.79 volumetric molar concentration.Be 1 by Fe/P mol ratio, by phosphoric acid H
3pO
4add in rich iron leach liquor, after 50 DEG C of heated and stirred 0.8h, then add the oxydol H of 0.475 times of ferrous iron molar weight
2o
2stirring reaction 30min, adding ammoniacal liquor regulator solution system pH is 3, reacts 3h further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor---tertiary iron phosphate FePO
4powder.
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the 2.265g tertiary iron phosphate FePO of gained in step (2)
4with 0.555gLi
2cO
3, 1.715g sucrose mixes, in atmosphere furnace, 750 DEG C of calcining 10h under protection of inert gas, take out after cooling, namely obtain LiFePO
4/ C positive electrode material.
(4) lithium titanate precursor-peroxide titanium compound is prepared:
To the rich titanium of step (1) gained leach add 12.5wt% weak ammonia in filter residue after 50 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 6, then under vigorous stirring, leach filter residue by every gram of rich titanium and add 4mlH
2o
2, supplementary ammoniacal liquor stablizes pH value to 6, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 1.5h, filter and obtain leach liquor, by leach liquor 110 DEG C heating evaporate to dryness, obtain faint yellow xerogel, be lithium titanate precursor-peroxide titanium compound.Crossing filter residue is SILICA FUME.
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
By step (4) gained peroxide titanium compound in 500 DEG C of calcining 4h, obtain TiO
2powder; By 6gTiO
2with 2.22gLi
2cO
3mix, in air, 800 DEG C of calcining 8h, namely obtain lithium titanate Li after furnace cooling
4ti
5o
12negative electrode material powder.
See Fig. 4 a and Fig. 4 b, be respectively the LiFePO of the present embodiment gained
4and Li
4ti
5o
12sEM figure.
Embodiment 4
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 30%, the mass ratio of hydrochloric acid and vanadium extraction waste is 1.5, extraction temperature 100 DEG C, and extraction time is 3h; After leaching completes, gained slurry is cooled to room temperature, filters and obtain Fu Tie leaching filtrate and rich titanium leaching filter residue.
(2) ferric lithium phosphate precursor-tertiary iron phosphate is prepared:
Steaming acid recovery process is carried out to HCl free in step (1) gained leach liquor, obtains concentrated leach liquor, be mixed with the rich iron leach liquor of 0.20 volumetric molar concentration.Be 0.80 by Fe/P mol ratio, by phosphoric acid H
3pO
4add in rich iron leach liquor, after 40 DEG C of heated and stirred 0.6h, then add the oxydol H of 0.49 times of ferrous iron molar weight
2o
2stirring reaction 20min, adding ammoniacal liquor regulator solution system pH is 2.5, reacts 2h further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor-tertiary iron phosphate FePO
4powder.
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the 2.265g tertiary iron phosphate FePO of gained in step (2)
4with 0.555gLi
2cO
3and 0.608g starch and 0.676g glucose mix, in atmosphere furnace, 720 DEG C of calcining 9h under protection of inert gas, take out after cooling, namely obtain LiFePO
4/ C positive electrode material.
(4) lithium titanate precursor-peroxide titanium compound is prepared:
To the rich titanium of step (1) gained leach add 12.5wt% weak ammonia in filter residue after 60 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 5, then under vigorous stirring, leach filter residue by every gram of rich titanium and add 3mlH
2o
2, supplementary ammoniacal liquor stablizes pH value to 5, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 1h, filter and obtain leach liquor, by leach liquor 100 DEG C heating evaporate to dryness, obtain faint yellow xerogel, be lithium titanate precursor-peroxide titanium compound.Crossing filter residue is SILICA FUME.
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
By step (4) gained peroxide titanium compound in 600 DEG C of calcining 3h, obtain TiO
2powder; By 6gTiO
2with 2.22gLi
2cO
3mix, in air, 760 DEG C of calcining 6h, namely obtain lithium titanate Li after furnace cooling
4ti
5o
12negative electrode material powder.
See Fig. 5 a and Fig. 5 b, be respectively the LiFePO of the present embodiment gained
4and Li
4ti
5o
12sEM figure.
Embodiment 5
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 25%, the mass ratio of hydrochloric acid and vanadium extraction waste is 3, extraction temperature 80 DEG C, and extraction time is 4h; After leaching completes, gained slurry is cooled to room temperature, filters and obtain Fu Tie leaching filtrate and rich titanium leaching filter residue.
(2) ferric lithium phosphate precursor-tertiary iron phosphate is prepared:
Steaming acid recovery process is carried out to HCl free in step (1) gained leach liquor, obtains concentrated leach liquor, be mixed with the rich iron leach liquor of 0.35 volumetric molar concentration.Be 0.90 by Fe/P mol ratio, by phosphoric acid H
3pO
4add in rich iron leach liquor, after 60 DEG C of heated and stirred 0.7h, then add the oxydol H of 0.52 times of ferrous iron molar weight
2o
2stirring reaction 15min, adding ammoniacal liquor regulator solution system pH is 3.5, reacts 4h further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor-tertiary iron phosphate FePO
4powder.
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the 2.265g tertiary iron phosphate FePO of gained in step (2)
4with 0.555gLi
2cO
3and 1.285g sucrose and 0.776 glucose mix, in atmosphere furnace, 730 DEG C of calcining 11h under protection of inert gas, take out after cooling, namely obtain LiFePO
4/ C positive electrode material.
(4) lithium titanate precursor-peroxide titanium compound is prepared:
To the rich titanium of step (1) gained leach add 12.5wt% weak ammonia in filter residue after 60 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 7, then under vigorous stirring, leach filter residue by every gram of rich titanium and add 5mlH
2o
2, supplementary ammoniacal liquor stablizes pH value to 7, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 1h, filter and obtain leach liquor, by leach liquor 100 DEG C heating evaporate to dryness, obtain faint yellow xerogel, be lithium titanate precursor-peroxide titanium compound.Crossing filter residue is SILICA FUME.
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
By step (4) gained peroxide titanium compound in 500 DEG C of calcining 4h, obtain TiO
2powder; By 6gTiO
2with 2.22gLi
2cO
3mix, in air, 810 DEG C of calcining 7h, namely obtain lithium titanate Li after furnace cooling
4ti
5o
12negative electrode material powder.
See Fig. 6 a and Fig. 6 b, be respectively the LiFePO of the present embodiment gained
4and Li
4ti
5o
12sEM figure.
Embodiment 6
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 28%, the mass ratio of hydrochloric acid and vanadium extraction waste is 2.65, extraction temperature 75 DEG C, and extraction time is 2.5h; After leaching completes, gained slurry is cooled to room temperature, filters and obtain Fu Tie leaching filtrate and rich titanium leaching filter residue.
(2) ferric lithium phosphate precursor-tertiary iron phosphate is prepared:
Steaming acid recovery process is carried out to HCl free in step (1) gained leach liquor, obtains concentrated leach liquor, be mixed with the rich iron leach liquor of 0.425 volumetric molar concentration.Be 0.85 by Fe/P mol ratio, by phosphoric acid H
3pO
4add in rich iron leach liquor, after 35 DEG C of heated and stirred 0.9h, then add the oxydol H of 0.54 times of ferrous iron molar weight
2o
2stirring reaction 25min, adding ammoniacal liquor regulator solution system pH is 3.5, reacts 1.5h further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor---tertiary iron phosphate FePO
4powder.
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the 2.265g tertiary iron phosphate FePO of gained in step (2)
4with 0.555gLi
2cO
3and 1.285g rock sugar mixes, in atmosphere furnace, 770 DEG C of calcining 12h under protection of inert gas, take out after cooling, namely obtain LiFePO
4/ C positive electrode material.
(4) lithium titanate precursor-peroxide titanium compound is prepared:
To the rich titanium of step (1) gained leach add 12.5wt% weak ammonia in filter residue after 35 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 4.5, then under vigorous stirring, leach filter residue by every gram of rich titanium and add 2.5mlH
2o
2, supplementary ammoniacal liquor stablizes pH value to 4.5, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 1h, filter and obtain leach liquor, by leach liquor 100 DEG C heating evaporate to dryness, obtain faint yellow xerogel, be lithium titanate precursor-peroxide titanium compound.Crossing filter residue is SILICA FUME.
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
By step (4) gained peroxide titanium compound in 500 DEG C of calcining 4h, obtain TiO
2powder; By 6gTiO
2with 2.22gLi
2cO
3mix, in air, 780 DEG C of calcining 9h, namely obtain lithium titanate Li after furnace cooling
4ti
5o
12negative electrode material powder.
See Fig. 7 a and Fig. 7 b, be respectively the LiFePO of the present embodiment gained
4and Li
4ti
5o
12sEM figure.
Embodiment 7
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 19%, the mass ratio of hydrochloric acid and vanadium extraction waste is 2.35, extraction temperature 85 DEG C, and extraction time is 3.5h; After leaching completes, gained slurry is cooled to room temperature, filters and obtain Fu Tie leaching filtrate and rich titanium leaching filter residue.
(2) ferric lithium phosphate precursor-tertiary iron phosphate is prepared:
Steaming acid recovery process is carried out to HCl free in step (1) gained leach liquor, obtains concentrated leach liquor, be mixed with the rich iron leach liquor of 0.65 volumetric molar concentration.Be 0.95 by Fe/P mol ratio, by phosphoric acid H
3pO
4add in rich iron leach liquor, after 45 DEG C of heated and stirred 0.5h, then add the oxydol H of 0.46 times of ferrous iron molar weight
2o
2stirring reaction 20min, adding ammoniacal liquor regulator solution system pH is 4, reacts 2.5h further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor-tertiary iron phosphate FePO
4powder.
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the 2.265g tertiary iron phosphate FePO of gained in step (2)
4, 0.555gLi
2cO
3and 3.369g agar powder mixes, in atmosphere furnace, 780 DEG C of calcining 13h under protection of inert gas, take out after cooling, namely obtain LiFePO
4/ C positive electrode material.
(4) lithium titanate precursor-peroxide titanium compound is prepared:
To the rich titanium of step (1) gained leach add 12.5wt% weak ammonia in filter residue after 45 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 5.5, then under vigorous stirring, leach filter residue by every gram of rich titanium and add 3.5mlH
2o
2, supplementary ammoniacal liquor stablizes pH value to 5.5, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 1h, filter and obtain leach liquor, by leach liquor 100 DEG C heating evaporate to dryness, obtain faint yellow xerogel, be lithium titanate precursor-peroxide titanium compound.Crossing filter residue is SILICA FUME.
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
By step (4) gained peroxide titanium compound in 500 DEG C of calcining 4h, obtain TiO
2powder; By 6gTiO
2with 2.22gLi
2cO
3mix, in air, 790 DEG C of calcining 6.5h, namely obtain lithium titanate Li after furnace cooling
4ti
5o
12negative electrode material powder.
See Fig. 8 a and Fig. 8 b, be respectively the LiFePO of the present embodiment gained
4and Li
4ti
5o
12sEM figure.
Embodiment 8
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 23%, the mass ratio of hydrochloric acid and vanadium extraction waste is 2.725, extraction temperature 95 DEG C, and extraction time is 4.5h; After leaching completes, gained slurry is cooled to room temperature, filters and obtain Fu Tie leaching filtrate and rich titanium leaching filter residue.
(2) ferric lithium phosphate precursor is prepared---tertiary iron phosphate:
Steaming acid recovery process is carried out to HCl free in step (1) gained leach liquor, obtains concentrated leach liquor, be mixed with the rich iron leach liquor of 0.375 volumetric molar concentration.Be 0.925 by Fe/P mol ratio, by phosphoric acid H
3pO
4add in rich iron leach liquor, after 55 DEG C of heated and stirred 0.6h, then add the oxydol H of 0.55 times of ferrous iron molar weight
2o
2stirring reaction 30min, adding ammoniacal liquor regulator solution system pH is 3, reacts 3h further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor---tertiary iron phosphate FePO
4powder.
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the 2.265g tertiary iron phosphate FePO of gained in step (2)
4with 0.555gLi
2cO
3and 5.485g gelatin mixes, in atmosphere furnace, 740 DEG C of calcining 14h under protection of inert gas, take out after cooling, namely obtain LiFePO
4/ C positive electrode material.
(4) lithium titanate precursor-peroxide titanium compound is prepared:
To the rich titanium of step (1) gained leach add 12.5wt% weak ammonia in filter residue after 55 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 6.5, then under vigorous stirring, leach filter residue by every gram of rich titanium and add 4.5mlH
2o
2, supplementary ammoniacal liquor stablizes pH value to 6.5, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 1h, filter and obtain leach liquor, by leach liquor 100 DEG C heating evaporate to dryness, obtain faint yellow xerogel, be lithium titanate precursor-peroxide titanium compound.Crossing filter residue is SILICA FUME.
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
By step (4) gained peroxide titanium compound in 500 DEG C of calcining 4h, obtain TiO
2powder; By 6gTiO
2with 2.22gLi
2cO
3mix, in air, 820 DEG C of calcining 7.5h, namely obtain lithium titanate Li after furnace cooling
4ti
5o
12negative electrode material powder.
See Fig. 9 a and Fig. 9 b, be respectively the LiFePO of the present embodiment gained
4and Li
4ti
5o
12sEM figure.
Embodiment 9
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 31%, the mass ratio of hydrochloric acid and vanadium extraction waste is 2.0, extraction temperature 105 DEG C, and extraction time is 3h; After leaching completes, gained slurry is cooled to room temperature, filters and obtain Fu Tie leaching filtrate and rich titanium leaching filter residue.
(2) ferric lithium phosphate precursor-tertiary iron phosphate is prepared:
Steaming acid recovery process is carried out to HCl free in step (1) gained leach liquor, obtains concentrated leach liquor, be mixed with the rich iron leach liquor of 0.75 volumetric molar concentration.Be 0.97 by Fe/P mol ratio, by phosphoric acid H
3pO
4add in rich iron leach liquor, after 65 DEG C of heated and stirred 1h, then add the oxydol H of 0.47 times of ferrous iron molar weight
2o
2stirring reaction 10min, adding ammoniacal liquor regulator solution system pH is 4, reacts 5h further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor---tertiary iron phosphate FePO
4powder.
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the 2.265g tertiary iron phosphate FePO of gained in step (2)
4with 0.555gLi
2cO
3and 1.043g citric acid mixes, in atmosphere furnace, 810 DEG C of calcining 8h under protection of inert gas, take out after cooling, namely obtain LiFePO
4/ C positive electrode material.
(4) lithium titanate precursor-peroxide titanium compound is prepared:
To the rich titanium of step (1) gained leach add 12.5wt% weak ammonia in filter residue after 65 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 7.5, then under vigorous stirring, leach filter residue by every gram of rich titanium and add 5.5mlH
2o
2, supplementary ammoniacal liquor stablizes pH value to 7.5, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 1h, filter and obtain leach liquor, by leach liquor 100 DEG C heating evaporate to dryness, obtain faint yellow xerogel, be lithium titanate precursor-peroxide titanium compound.Crossing filter residue is SILICA FUME.
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
By step (4) gained peroxide titanium compound in 500 DEG C of calcining 4h, obtain TiO
2powder; By 6gTiO
2with 2.22gLi
2cO
3mix, in air, 770 DEG C of calcining 8.5h, namely obtain lithium titanate Li after furnace cooling
4ti
5o
12negative electrode material powder.
See Figure 10 a and Figure 10 b, be respectively the LiFePO of the present embodiment gained
4and Li
4ti
5o
12sEM figure.
Embodiment 10
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 15%, the mass ratio of hydrochloric acid and vanadium extraction waste is 2.125, extraction temperature 70 DEG C, and extraction time is 2h; After leaching completes, gained slurry is cooled to room temperature, filters and obtain Fu Tie leaching filtrate and rich titanium leaching filter residue.
(2) ferric lithium phosphate precursor-tertiary iron phosphate is prepared:
Steaming acid recovery process is carried out to HCl free in step (1) gained leach liquor, obtains concentrated leach liquor, be mixed with the rich iron leach liquor of 0.265 volumetric molar concentration.Be 0.75 by Fe/P mol ratio, by phosphoric acid H
3pO
4add in rich iron leach liquor, after 30 DEG C of heated and stirred 0.5h, then add the oxydol H of 0.45 times of ferrous iron molar weight
2o
2stirring reaction 10min, adding ammoniacal liquor regulator solution system pH is 2, reacts 1h further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor-tertiary iron phosphate FePO
4powder.
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the 2.265g tertiary iron phosphate FePO of gained in step (2)
4with 0.555gLi
2cO
3and 1.184g agar powder, 2.241g gelatin, 0.361g citric acid and 0.642g rock sugar mix, in atmosphere furnace, 700 DEG C of calcining 8h under protection of inert gas, take out after cooling, namely obtain LiFePO
4/ C positive electrode material.
(4) lithium titanate precursor-peroxide titanium compound is prepared:
To the rich titanium of step (1) gained leach add 12.5wt% weak ammonia in filter residue after 70 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 4, then under vigorous stirring, leach filter residue by every gram of rich titanium and add 2mlH
2o
2, supplementary ammoniacal liquor stablizes pH value to 4, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 1h, filter and obtain leach liquor, by leach liquor 100 DEG C heating evaporate to dryness, obtain faint yellow xerogel, be lithium titanate precursor-peroxide titanium compound.Crossing filter residue is SILICA FUME.
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
By step (4) gained peroxide titanium compound in 500 DEG C of calcining 4h, obtain TiO
2powder; By 6gTiO
2with 2.22gLi
2cO
3mix, in air, 830 DEG C of calcining 9.5h, namely obtain lithium titanate Li after furnace cooling
4ti
5o
12negative electrode material powder.
See Figure 11 a and Figure 11 b, be respectively the LiFePO of the present embodiment gained
4and Li
4ti
5o
12sEM figure.
Although last it is noted that described the present invention and advantage thereof in detail above, be to be understood that and can carry out various change when not exceeding the spirit and scope of the present invention limited by appended claim, substituting and converting.And scope of the present invention is not limited only to the specific embodiment of process, equipment, means, method and step described by specification sheets.One of ordinary skilled in the art will readily appreciate that from disclosure of the present invention, can use perform the function substantially identical with corresponding embodiment described herein or obtain and its substantially identical result, existing and that will be developed in the future process, equipment, means, method or step according to the present invention.Therefore, appended claim is intended to comprise such process, equipment, means, method or step in their scope.
Claims (8)
1. vanadium extraction waste prepares a method for electrode material of lithium battery iron lithium phosphate and lithium titanate, it is characterized in that, comprises the following steps:
(1) ferrotitanium is separated:
After vanadium extraction waste Mechanical Crushing, with Leaching in Hydrochloric Acid vanadium extraction waste, leach rear filtration and obtained Fu Tie leaching filtrate and rich titanium leaching filter residue;
(2) ferric lithium phosphate precursor is prepared:
Free HCl in filtrate is leached to the rich iron of step (1) gained and carries out steaming acid recovery process, obtain concentrated leach liquor, be mixed with rich iron leach liquor; By precipitation agent phosphoric acid H
3pO
4add in rich iron leach liquor, then add oxidant hydrogen peroxide H
2o
2stirring reaction, adds ammoniacal liquor regulator solution system pH, reacts further, gained sedimentation and filtration washing and drying, namely obtains ferric lithium phosphate precursor-tertiary iron phosphate FePO
4powder;
(3) iron lithium phosphate LiFePO is prepared
4anode material for lithium secondary battery:
By the tertiary iron phosphate FePO of gained in step (2)
4presoma and Li
2cO
3and organic carbon source mixes, calcine under protection of inert gas in atmosphere furnace, take out after cooling, namely obtain LiFePO
4/ C positive electrode material;
(4) lithium titanate precursor is prepared:
Filter residue is leached to the rich titanium of gained in step (1) and adds NH
3h
2o, heats and stirs, then adding H
2o
2, adding H
2o
2constantly drip ammoniacal liquor adjust ph in process, then add dense H
2sO
4continue reaction, filter out filtrate, by filtrate reacting by heating, lighter is to oyster white, and evaporate to dryness obtains faint yellow xerogel, is lithium titanate precursor-peroxide titanium compound; Crossing filter residue is SILICA FUME;
(5) lithium titanate Li is prepared
4ti
5o
12lithium secondary battery cathode material:
Step (4) gained peroxide titanium compound is calcined, obtains TiO
2powder; By TiO
2powder and Li
2cO
3mix, calcine in air, after furnace cooling, namely obtain lithium titanate Li
4ti
5o
12negative electrode material powder.
2. method according to claim 1, is characterized in that:
In described step (1): leach vanadium extraction waste at ambient pressure with the hydrochloric acid of mass concentration 15-35%, the mass ratio of hydrochloric acid and vanadium extraction waste is 1.5-3.0, extraction temperature 70-110 DEG C, and extraction time is 1-5h; After leaching completes, gained slurry is cooled to room temperature, then filters.
3. method according to claim 1, is characterized in that:
In described step (2): concentrated leach liquor is mixed with the rich iron leach liquor of 0.2-0.8 volumetric molar concentration; Adding ammoniacal liquor regulator solution system pH is 2-4;
After adding phosphoric acid, after 30-70 DEG C of heated and stirred 0.5-1h, then add oxygenant stirring reaction 5-30min; Add the follow-up continuous reaction 1-5h of ammoniacal liquor;
Wherein, in solution, the add-on of divalence Fe molar weight and precipitation agent is Fe/P mol ratio 0.75-1:1, and the add-on of oxygenant is 0.45-0.55 times of divalence Fe molar weight in solution.
4. method according to claim 1, is characterized in that:
In described step (3): described tertiary iron phosphate FePO
4presoma and Li
2cO
3and mol ratio 2:1:(0.5 ~ 1 of organic carbon source);
The temperature of calcining in described atmosphere furnace is 700-800 DEG C, and calcination time is 8-15h.
5. method according to claim 1, is characterized in that:
In described step (4):
After adding 12.5wt% weak ammonia 30-70 DEG C of heated and stirred to presenting white suspension liquid, continuing to drip 12.5wt% weak ammonia adjust ph is 4-8, then under agitation, leaches filter residue add 2-6mlH by every gram of rich titanium
2o
2, supplementary ammoniacal liquor stablizes pH value to set(ting)value, adds dense H
2sO
4be orange-yellow to suspension liquid, continue reaction 0.5-1.5h, filter and obtain leach liquor, by leach liquor 90-110 DEG C of heating evaporate to dryness, obtain peroxide titanium compound.
6. method according to claim 1, is characterized in that:
In described step (5):
The calcining temperature of described peroxide titanium compound is 400-600 DEG C of calcining 3-5h; Described TiO
2powder and Li
2cO
3mix by Li:Ti mol ratio 4:5, in described air, calcining temperature is 750-850 DEG C, and calcination time is 5-10h.
7. the method according to any one of claim 1-6, is characterized in that, described iron lithium phosphate LiFePO
4anode material for lithium secondary battery organic carbon source used is selected from least one in glucose, starch, sucrose, agar powder, gelatin, citric acid and rock sugar.
8. battery electrode material iron lithium phosphate and a lithium titanate, is characterized in that, prepares according to the method described in any one of claim 1-7.
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| CN113924374A (en) * | 2019-04-15 | 2022-01-11 | 诺斯伏特公司 | Method for recovering cathode material in battery recycling |
| CN113851618A (en) * | 2021-08-10 | 2021-12-28 | 桂林理工大学 | Method for preparing high-performance iron phosphate/graphene composite negative electrode material by using iron vitriol slag hydrochloric acid leaching solution and application |
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