CN105854884B - The method that lithium battery anode waste material is handled - Google Patents
The method that lithium battery anode waste material is handled Download PDFInfo
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- CN105854884B CN105854884B CN201610185743.XA CN201610185743A CN105854884B CN 105854884 B CN105854884 B CN 105854884B CN 201610185743 A CN201610185743 A CN 201610185743A CN 105854884 B CN105854884 B CN 105854884B
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- battery anode
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910032387 LiCoO2 Inorganic materials 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910012820 LiCoO Inorganic materials 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 26
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000012153 distilled water Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 31
- 229910007966 Li-Co Inorganic materials 0.000 claims description 25
- 229910008295 Li—Co Inorganic materials 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 19
- 238000006555 catalytic reaction Methods 0.000 claims description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 68
- 229910012923 LiCoO2In Inorganic materials 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000000103 photoluminescence spectrum Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Hybrid Cells (AREA)
- Primary Cells (AREA)
Abstract
The present invention provides the methods that a kind of pair of lithium battery anode waste material is handled comprising following steps: by anode waste LiCoO2It is purified, obtains the high-purity LiCoO that purity is not less than 98~99%2Powder；By the high-purity LiCoO2After powder is dissolved by heating with concentrated nitric acid, it is evaporated nitric acid, dehydrated alcohol and distilled water is added, after mixing, obtains containing Li+And Co3+Solution, adjust the solution pH value be 0.1~0.3；Titanium source is added, after mixing, hydro-thermal reaction is carried out at 140~220 DEG C, collects precipitating and cleans, is dry, calcined at 300~600 DEG C, collect product.Compared with prior art, the present invention is with following the utility model has the advantages that the present invention utilizes lithium battery anode waste material LiCoO2In Li and Co adulterate TiO2, obtain efficient photochemical catalyst；High-value-use LiCoO2, utilized for its waste resource recovery and provide a new approach.
Description
Technical field
The invention belongs to lithium battery anode waste material LiCoO2Resource utilization field, and in particular, to a kind of to utilize lithium electricity
Pond anode waste LiCoO2It prepares Li-Co and adulterates TiO2The method of catalysis material.
Background technique
Lithium battery is widely used in the portable electronic products such as mobile phone, laptop at present.With these electronic products
Largely use and overstock, the safe handling of lithium battery causes people and more and more pays close attention to.Anode material of lithium battery is it
One of four big critical materials (anode, cathode, electrolyte and diaphragm).LiCoO2It is often used as anode material of lithium battery active matter
Matter, because its specific capacity is high, performance is stablized.But work as this LiCoO2After lithium battery is scrapped, need to itself Li and Co metal into
Row resource utilization or recycling.If dealing with improperly, it will generation environment pollution damages human health.
For lithium battery anode waste material LiCoO2Processing reverse reclamation method, reparative regeneration LiCoO is usually used2Material
Material.(101383442 A of CN) is obtained from discarded anode material of lithium battery containing LiCoO in long east of Lee et al.2Coarse fodder removes it
Alkali cleaning obtains the higher LiCoO of purity after binder and acetylene black2, then be incorporated certain lithium carbonate and had through high-temperature calcination
Active LiCoO2Electrode material.Citric acid and dual oxide water are added to lithium battery by Zheng Ying et al. (103474718 A of CN)
LiCoO2Filtrate containing Co is obtained in waste material, successively obtains available LiCoO after ammonium oxalate precipitating and lithium carbonate supplement lithium ion2
Electrode material powder.He Wen intelligence et al. (102344172 A of CN) is by LiCoO2Waste material is added in lithium hydroxide solution, through super
The LiCoO that sound is repaired2Material.Reverse reclamation LiCoO2Have the advantages that can be recycled, but LiCoO2Quality can be
It reduces, its service life is caused to greatly reduce.In order to preferably utilize lithium battery anode waste material LiCoO2, this patent propose with
LiCoO2In Li and Co adulterate TiO simultaneously2, prepare the photocatalysis that there is wide spectrum to absorb solar energy and high efficiency photocatalysis performance
Material, while a new method is provided for the resource utilization of waste lithium cell positive electrode.
Summary of the invention
For existing lithium battery anode waste material LiCoO2The deficiency of processing technique, the object of the present invention is to provide a kind of utilizations
Lithium battery anode waste material is handled, to obtain a kind of Li-Co doping TiO2The method of catalysis material.
The present invention is achieved by the following technical solutions:
In a first aspect, the present invention provides a kind of couple of lithium battery anode waste material LiCoO2The method handled comprising
Following steps:
By LiCoO2It is purified, obtains the high-purity LiCoO that purity is not less than 98~99%2Powder；If purity is not achieved
This range, it will introduce excessive impurity, reduce the photocatalysis performance of target material；
By the high-purity LiCoO2After powder is dissolved by heating with concentrated nitric acid, be evaporated nitric acid, be added dehydrated alcohol and
Distilled water after mixing, is obtained containing Li+And Co3+Solution, adjust the solution pH value be 0.1~0.3；If peracid will
The hydrolysis for slowing down titanium source below, makes TiO2Yield is reduced；And TiO will be made by crossing alkali2Crystal grain is excessively grown up, and photocatalysis performance is reduced；
Titanium source is added, after mixing, carries out hydro-thermal reaction at 140~220 DEG C, collects precipitating and cleans, is dry, 300~
It is calcined at 600 DEG C, collects product；Hydro-thermal reaction need to control certain temperature, if temperature is too low, TiO2Crystal form it is poor；
Temperature is excessively high to bring safety issue；Calcination temperature is also required to control range, and temperature is too low, cannot get anatase TiO2；Temperature
Height is spent, then can generate excessive Rutile Type TiO2, eventually reduce the photocatalysis performance of target material.
Preferably, the hydro-thermal reaction is carried out in the reaction kettle with stainless steel polytetrafluoroethylliner liner
's.
Preferably, by LiCoO2The step of being purified specifically includes following operation:
The lithium battery anode waste material LiCoO of binder, conductive agent and foreign metal will be removed2It is mixed with dehydrated alcohol
It closes, is handled under ultrasonic conditions, then carry out eccentric cleaning with distilled water, drying obtains the LiCoO of high-purity2Powder
End.
Preferably, the mass ratio of the lithium battery anode waste material and dehydrated alcohol is 1:(3~10)；Dehydrated alcohol
Main function be cleaning organic matter matter, if additional amount is too low, the impurity-eliminating effect being not achieved, to can generate excessive miscellaneous
Matter；If additional amount is excessive, the difficulty of subsequent centrifuge separation can be increased.
Preferably, the high-purity LiCoO2The mass ratio of powder and concentrated nitric acid is 1:(3~5)；If being higher than this
A range, then LiCoO2Powder cannot be completely dissolved；If being lower than this range, it will cause the waste of acid, also will increase subsequent
The difficulty of evaporation.
Preferably, the mass fraction of the concentrated nitric acid is not less than 65wt%.
Preferably, the Li+Molar ratio with titanium source is (0.01~0.2): 1；Within this range, it just can guarantee
Suitable doping concentration, and too low or excessively high molar ratio cannot all improve the photocatalysis performance of target material.
Preferably, the volume ratio of the dehydrated alcohol and distilled water is 2:1；Under this ratio, it can obtain best
The TiO of size and shape2Crystal grain, to guarantee efficient photocatalysis performance.
Preferably, described to contain Li+And Co3+Solution in, Li+The concentration of ion is 0.22~4.32mg/L,
Co3+The concentration of ion is 0.20~4.25mg/L.
Preferably, the titanium source is one or both of tetraisopropyl titanate, tetrabutyl titanate.
Preferably, the time of the hydro-thermal reaction is 6~40h；Hydro-thermal reaction needs to control the suitable time, if
Time is too short, can make TiO2Crystal property it is bad；If overlong time, TiO can be made2Excessive grain is grown up.
Second aspect the present invention also provides a kind of Li-Co that the processing method by front obtains while adulterating TiO2
Catalysis material.
The principle of the method for the present invention is according to lithium battery anode waste material LiCoO2Ingredient, preparation Li and Co adulterate simultaneously
TiO2Catalysis material, this material has Li concurrently and Co individually adulterates TiO2Advantage.Li can inhibit TiO2Crystal grain is grown up,
Increase TiO2Specific surface area, improve TiO2Absorption property.Co can expand TiO2ABSORPTION EDGE, make it have higher efficiency
Sunlight capture ability.Li-Co is adulterated simultaneously also can increase TiO2Light induced electron and hole separative efficiency, it is right finally to improve its
The degradation efficiency of waste water from dyestuff.Use lithium battery anode waste material LiCoO2, it is ensured that its higher purity.In preparation process for
Remove the lithium battery anode waste material LiCoO of binder, conductive agent and foreign metal2First carry out high-power ultrasonic cleaning.With adding
The concentrated nitric acid of heat can both dissolve LiCoO2, obtain the nitrate of Li and Co, moreover it is possible to further remove impurity.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, the present invention utilizes lithium battery anode waste material LiCoO2In Li and Co adulterate TiO2, obtain efficient photochemical catalyst.
2, high-value-use LiCoO2, utilized for its waste resource recovery and provide a new approach.
3, the Li-Co obtained adulterates TiO2ABSORPTION EDGE can reach 700nm, specific surface area can reach 200m2/ g, hence it is evident that
Higher than pure TiO2Value (60m2/g).Under xenon lamp irradiation, Li-Co adulterates TiO2All to the degradation rate of methylene blue and methyl orange
Much higher than pure TiO2Value.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
The present invention provides a kind of method handled using lithium battery anode waste material, and embodiment is set forth below to the present invention
It is described in further detail:
Embodiment 1
Step 1 will remove the lithium battery anode waste material LiCoO of binder, conductive agent and foreign metal2By solid-liquid quality
Than dehydrated alcohol and high-power ultrasonic cleaning is added for 1:3,60 DEG C of vacuum dryings obtain purity after distilled water eccentric cleaning
For 99% LiCoO2Powder；
Step 2 takes LiCoO obtained by step 12Powder is that 1:3 is added to the burning containing 65% concentrated nitric acid by solid-liquid mass ratio
In cup, 100 DEG C are warming up in ventilating kitchen makes LiCoO2It is completely dissolved and is evaporated concentrated nitric acid；
Dehydrated alcohol and distilled water are added in step 2 beaker by solid-liquid mass ratio for 1:10, are continuously stirred by step 3
After mixing 30 minutes, its pH value is transferred to 0.1 using 65% concentrated nitric acid；
The volume ratio of the dehydrated alcohol and distilled water is 2:1；
The Li+The concentration of ion is 0.22mg/L, Co3+The concentration of ion is 0.20mg/L；
Step 4 is slowly added to tetraisopropyl titanate in the clarified solution that step 3 obtains, and continuously stirs 1 hour；
The tetraisopropyl titanate and Li+The molar ratio of ion is 1:0.01；
It is anti-to be transferred to 140 DEG C of hydro-thermals in stainless steel polytetrafluoroethylliner liner by step 5 for the resulting colloidal solution of step 4
It answers 6 hours；
Step 6, by the 60 DEG C of drying after deionized water and washes of absolute alcohol of the resulting precipitating of step 5, and at 300 DEG C
Lower calcining obtains Li-Co while adulterating TiO for 6 hours2Catalysis material.
Resource utilization lithium battery anode waste material LiCoO of the present invention2In Li and Co as dopant, obtain Li-Co
Adulterate TiO2Catalysis material.Relative to pure TiO2, the optical absorption intensity of resulting materials is remarkably reinforced, and ABSORPTION EDGE is extended to
500nm, specific surface area increase to 120m2/g.Photoluminescence spectrum intensity of the resulting materials under 300nm excitation is significantly lower than pure TiO2,
Illustrate it with better light induced electron and hole separating capacity.It is irradiated in 3 hours in 500W xenon lamp, Li-Co adulterates TiO2It is right
Methylene blue and the degradation rate of methyl orange are respectively 90% and 82%, are higher than pure TiO2Respective value (46% and 35%).
Embodiment 2
Step 1 will remove the lithium battery anode waste material LiCoO of binder, conductive agent and foreign metal2By solid-liquid quality
Than dehydrated alcohol and high-power ultrasonic cleaning is added for 1:10,60 DEG C of vacuum dryings obtain purity after distilled water eccentric cleaning
For 98% LiCoO2Powder；
Step 2 takes LiCoO obtained by step 12Powder is that 1:5 is added to the burning containing 65% concentrated nitric acid by solid-liquid mass ratio
In cup, 100 DEG C are warming up in ventilating kitchen makes LiCoO2It is completely dissolved and is evaporated concentrated nitric acid；
Dehydrated alcohol and distilled water are added in step 2 beaker by solid-liquid mass ratio for 1:10, are continuously stirred by step 3
After mixing 30 minutes, its pH value is transferred to 0.3 using 65% concentrated nitric acid；
The volume ratio of the dehydrated alcohol and distilled water is 2:1；
The Li+The concentration of ion is 4.32mg/L, Co3+The concentration of ion is 4.25mg/L；
Step 4 is slowly added to tetrabutyl titanate in the clarified solution that step 3 obtains, and continuously stirs 1 hour；
The tetraisopropyl titanate and Li+The molar ratio of ion is 1:0.2；
It is anti-to be transferred to 220 DEG C of hydro-thermals in stainless steel polytetrafluoroethylliner liner by step 5 for the resulting colloidal solution of step 4
It answers 2 hours；
Step 6, by the 60 DEG C of drying after deionized water and washes of absolute alcohol of the resulting precipitating of step 5, and at 600 DEG C
Lower calcining obtains Li-Co while adulterating TiO for 2 hours2Catalysis material.
Resource utilization lithium battery anode waste material LiCoO of the present invention2In Li and Co as dopant, obtain Li-Co
Adulterate TiO2Catalysis material.Relative to pure TiO2, the optical absorption intensity of resulting materials is remarkably reinforced, and ABSORPTION EDGE is extended to
670nm, specific surface area increase to 195m2/g.Photoluminescence spectrum intensity of the resulting materials under 300nm excitation is significantly lower than pure TiO2,
Illustrate it with better light induced electron and hole separating capacity.It is irradiated in 3 hours in 500W xenon lamp, Li-Co adulterates TiO2It is right
Methylene blue and the degradation rate of methyl orange are respectively 99% and 95%, are higher than pure TiO2Respective value (65% and 56%).
Embodiment 3
Step 1 will remove the lithium battery anode waste material LiCoO of binder, conductive agent and foreign metal2By solid-liquid quality
Than dehydrated alcohol and high-power ultrasonic cleaning is added for 1:8,60 DEG C of vacuum dryings obtain purity after distilled water eccentric cleaning
For 99.5% LiCoO2Powder；
Step 2 takes LiCoO obtained by step 12Powder is that 1:4 is added to the burning containing 65% concentrated nitric acid by solid-liquid mass ratio
In cup, 100 DEG C are warming up in ventilating kitchen makes LiCoO2It is completely dissolved and is evaporated concentrated nitric acid；
Dehydrated alcohol and distilled water are added in step 2 beaker by solid-liquid mass ratio for 1:10, are continuously stirred by step 3
After mixing 30 minutes, its pH value is transferred to 0.2 using 65% concentrated nitric acid；
The volume ratio of the dehydrated alcohol and distilled water is 2:1；
The Li+The concentration of ion is 1.01mg/L, Co3+The concentration of ion is 0.92mg/L；
Step 4 is slowly added to tetraisopropyl titanate in the clarified solution that step 3 obtains, and continuously stirs 1 hour；
The tetraisopropyl titanate and Li+The molar ratio of ion is 1:0.05；
It is anti-to be transferred to 180 DEG C of hydro-thermals in stainless steel polytetrafluoroethylliner liner by step 5 for the resulting colloidal solution of step 4
It answers 4 hours；
Step 6, by the 60 DEG C of drying after deionized water and washes of absolute alcohol of the resulting precipitating of step 5, and at 450 DEG C
Lower calcining obtains Li-Co while adulterating TiO for 3 hours2Catalysis material.
Resource utilization lithium battery anode waste material LiCoO of the present invention2In Li and Co as dopant, obtain Li-Co
Adulterate TiO2Catalysis material.Relative to pure TiO2, the optical absorption intensity of resulting materials is remarkably reinforced, and ABSORPTION EDGE is extended to
610nm, specific surface area increase to 180m2/g.Photoluminescence spectrum intensity of the resulting materials under 300nm excitation is significantly lower than pure TiO2,
Illustrate it with better light induced electron and hole separating capacity.It is irradiated in 3 hours in 500W xenon lamp, Li-Co adulterates TiO2It is right
Methylene blue and the degradation rate of methyl orange are respectively 78% and 60%, are higher than pure TiO2Respective value (31% and 27%).
Embodiment 4
Step 1 will remove the lithium battery anode waste material LiCoO of binder, conductive agent and foreign metal2By solid-liquid quality
Than dehydrated alcohol and high-power ultrasonic cleaning is added for 1:5,60 DEG C of vacuum dryings obtain purity after distilled water eccentric cleaning
For 98.5% LiCoO2Powder；
Step 2 takes LiCoO obtained by step 12Powder is that 1:5 is added to the burning containing 65% concentrated nitric acid by solid-liquid mass ratio
In cup, 100 DEG C are warming up in ventilating kitchen makes LiCoO2It is completely dissolved and is evaporated concentrated nitric acid；
Dehydrated alcohol and distilled water are added in step 2 beaker by solid-liquid mass ratio for 1:10, are continuously stirred by step 3
After mixing 30 minutes, its pH value is transferred to 0.1 using 65% concentrated nitric acid；
The volume ratio of the dehydrated alcohol and distilled water is 2:1；
The Li+The concentration of ion is 2.16mg/L, Co3+The concentration of ion is 2.06mg/L；
Step 4 is slowly added to tetraisopropyl titanate in the clarified solution that step 3 obtains, and continuously stirs 1 hour；
The tetraisopropyl titanate and Li+The molar ratio of ion is 1:0.1；
It is anti-to be transferred to 200 DEG C of hydro-thermals in stainless steel polytetrafluoroethylliner liner by step 5 for the resulting colloidal solution of step 4
It answers 4 hours；
Step 6, by the 60 DEG C of drying after deionized water and washes of absolute alcohol of the resulting precipitating of step 5, and at 500 DEG C
Lower calcining obtains Li-Co while adulterating TiO for 3 hours2Catalysis material.
Resource utilization lithium battery anode waste material LiCoO of the present invention2In Li and Co as dopant, obtain Li-Co
Adulterate TiO2Catalysis material.Relative to pure TiO2, the optical absorption intensity of resulting materials is remarkably reinforced, and ABSORPTION EDGE is extended to
700nm, specific surface area increase to 200m2/g.Photoluminescence spectrum intensity of the resulting materials under 300nm excitation is significantly lower than pure TiO2,
Illustrate it with better light induced electron and hole separating capacity.It is irradiated in 3 hours in 500W xenon lamp, Li-Co adulterates TiO2It is right
Methylene blue and the degradation rate of methyl orange are respectively 98% and 90%, are higher than pure TiO2Respective value (56% and 45%).
Embodiment 5
Step 1 will remove the lithium battery anode waste material LiCoO of binder, conductive agent and foreign metal2By solid-liquid quality
Than dehydrated alcohol and high-power ultrasonic cleaning is added for 1:4,60 DEG C of vacuum dryings obtain purity after distilled water eccentric cleaning
For 99% LiCoO2Powder；
Step 2 takes LiCoO obtained by step 12Powder is that 1:3 is added to the burning containing 65% concentrated nitric acid by solid-liquid mass ratio
In cup, 100 DEG C are warming up in ventilating kitchen makes LiCoO2It is completely dissolved and is evaporated concentrated nitric acid；
Dehydrated alcohol and distilled water are added in step 2 beaker by solid-liquid mass ratio for 1:12, are continuously stirred by step 3
After mixing 30 minutes, its pH value is transferred to 0.1 using 65% concentrated nitric acid；
The volume ratio of the dehydrated alcohol and distilled water is 2:1；
The Li+The concentration of ion is 0.647mg/L, Co3+The concentration of ion is 0.645mg/L；
Step 4 is slowly added to tetraisopropyl titanate in the clarified solution that step 3 obtains, and continuously stirs 1 hour；
The tetraisopropyl titanate and Li+The molar ratio of ion is 1:0.03；
It is anti-to be transferred to 160 DEG C of hydro-thermals in stainless steel polytetrafluoroethylliner liner by step 5 for the resulting colloidal solution of step 4
It answers 4 hours；
Step 6, by the 60 DEG C of drying after deionized water and washes of absolute alcohol of the resulting precipitating of step 5, and at 400 DEG C
Lower calcining obtains Li-Co while adulterating TiO for 2 hours2Catalysis material.
Resource utilization lithium battery anode waste material LiCoO of the present invention2In Li and Co as dopant, obtain Li-Co
Adulterate TiO2Catalysis material.Relative to pure TiO2, the optical absorption intensity of resulting materials is remarkably reinforced, and ABSORPTION EDGE is extended to
660nm, specific surface area increase to 180m2/g.Photoluminescence spectrum intensity of the resulting materials under 300nm excitation is significantly lower than pure TiO2,
Illustrate it with better light induced electron and hole separating capacity.It is irradiated in 3 hours in 500W xenon lamp, Li-Co adulterates TiO2It is right
Methylene blue and the degradation rate of methyl orange are respectively 96% and 92%, are higher than pure TiO2Respective value (63% and 55%).
In conclusion the present invention utilizes lithium battery anode waste material LiCoO2In Li and Co adulterate TiO2, obtain efficient light
Catalyst；High-value-use LiCoO2, utilized for its waste resource recovery and provide a new approach；The Li-Co of acquisition is adulterated
TiO2ABSORPTION EDGE can reach 700nm, specific surface area can reach 200m2/ g, hence it is evident that be higher than pure TiO2Value (60m2/g).?
Under xenon lamp irradiation, Li-Co adulterates TiO2Pure TiO is much higher than to the degradation rate of methylene blue and methyl orange2Value.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (8)
1. the method that a kind of pair of lithium battery anode waste material is handled, which comprises the steps of:
Lithium battery anode waste material is purified, the high-purity LiCoO that purity is not less than 98 ~ 99% is obtained2Powder；
By the high-purity LiCoO2After powder is dissolved by heating with concentrated nitric acid, it is evaporated nitric acid, dehydrated alcohol and distillation is added
Water after mixing, is obtained containing Li+And Co3+Solution, adjust the solution pH value be 0.1 ~ 0.3；
Titanium source is added, after mixing, hydro-thermal reaction is carried out at 140 ~ 220 DEG C, collects precipitating and cleans, is dry, at 300 ~ 600 DEG C
It is calcined, collects product, is i.e. Li-Co adulterates TiO simultaneously2Catalysis material.
2. the method handled as described in claim 1 lithium battery anode waste material, which is characterized in that the high-purity
LiCoO2The mass ratio of powder and concentrated nitric acid is 1:(3 ~ 5).
3. the method handled as described in claim 1 lithium battery anode waste material, which is characterized in that the concentrated nitric acid
Mass fraction is not less than 65wt%.
4. the method handled as described in claim 1 lithium battery anode waste material, which is characterized in that the Li+With titanium source
Molar ratio be (0.01 ~ 0.2): 1.
5. the method handled as described in claim 1 lithium battery anode waste material, which is characterized in that the dehydrated alcohol
Volume ratio with distilled water is 2:1.
6. the method handled as described in claim 1 lithium battery anode waste material, which is characterized in that described to contain Li+With
Co3+Solution in, Li+The concentration of ion is 0.22 ~ 4.32mg/L, Co3+The concentration of ion is 0.20 ~ 4.25mg/L.
7. the method handled as described in claim 1 lithium battery anode waste material, which is characterized in that the titanium source is titanium
One or both of sour tetra-isopropyl, tetrabutyl titanate.
8. a kind of Li-Co adulterates TiO simultaneously2Catalysis material, which is characterized in that pass through any one of claim 1 ~ 7 institute
The processing method stated obtains.
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| CN103570344A (en) * | 2013-11-04 | 2014-02-12 | 河南师范大学 | Method for preparing manganese-zinc ferrite by using waste zinc-manganese battery |
| CN104611566A (en) * | 2014-12-29 | 2015-05-13 | 长沙矿冶研究院有限责任公司 | Method for recycling valuable metals in waste lithium ion batteries |
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| CN103285869A (en) * | 2013-05-08 | 2013-09-11 | 上海交通大学 | Method for preparing up-conversion photocatalytic material by utilizing electroplating waste water |
| CN103570344A (en) * | 2013-11-04 | 2014-02-12 | 河南师范大学 | Method for preparing manganese-zinc ferrite by using waste zinc-manganese battery |
| CN104611566A (en) * | 2014-12-29 | 2015-05-13 | 长沙矿冶研究院有限责任公司 | Method for recycling valuable metals in waste lithium ion batteries |
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