CN108147566A - A kind of method using waste lithium ion cell anode material catalytic degradation organic wastewater - Google Patents
A kind of method using waste lithium ion cell anode material catalytic degradation organic wastewater Download PDFInfo
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- CN108147566A CN108147566A CN201711398375.8A CN201711398375A CN108147566A CN 108147566 A CN108147566 A CN 108147566A CN 201711398375 A CN201711398375 A CN 201711398375A CN 108147566 A CN108147566 A CN 108147566A
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- organic wastewater
- positive electrode
- organic
- waste
- lithium ion
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- 238000006731 degradation reaction Methods 0.000 title claims abstract description 36
- 230000015556 catabolic process Effects 0.000 title claims abstract description 28
- 239000002351 wastewater Substances 0.000 title claims abstract description 27
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 8
- 239000010405 anode material Substances 0.000 title claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005416 organic matter Substances 0.000 claims abstract description 6
- 238000013021 overheating Methods 0.000 claims abstract description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical class OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims 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 claims description 4
- 239000005955 Ferric phosphate Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 229940032958 ferric phosphate Drugs 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 239000010815 organic waste Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 7
- 229910052493 LiFePO4 Inorganic materials 0.000 description 6
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 6
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 sulfate radical Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 239000010793 electronic waste Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a kind of methods using waste lithium ion cell anode material catalytic degradation organic wastewater;This method includes:Waste and old lithium ion battery is disassembled, takes out positive electrode, after Overheating Treatment, collects positive electrode powder, and launch and be used as Catalyst Adsorption for a period of time into organic wastewater solution.Tetravalence sulphur is put into later(S(
Description
Technical field
The invention belongs to Disposal of Electronic Wastes and technical field for the treatment of of organic waste, more particularly to tetravalence sulfosalt
Or single persulfate(PMS)High-level oxidation technology of the solution as oxidant.
Background technology
In recent years, the high-level oxidation technology based on radical reaction(Advanced Oxidation Processes,
AOPs), because it is with oxidability is strong, reaction rate is fast, selectivity is small, reaction condition is mild, flexibility is high and to organic dirt
The advantages that object mineralization rate is high is contaminated, quick development has been obtained in treatment of Organic Wastewater field.These free radicals include sulfate radical certainly
By base(SO4 •-), hydroxyl radical free radical(•OH), ultra-oxygen anion free radical(O2 •-)Deng.They will be big by way of electronics transfer
Molecular organic resolves into small organic molecule, then small organic molecule is decomposed into carbon dioxide and water.
Lithium ion battery with its have, small, light weight higher than energy, temperature limit is wide, self-discharge rate is low, follows
Ring long lifespan such as has a safety feature at the unique advantages, becomes the best battery system of current comprehensive performance, usage amount and scraps
Stage of the amount in rapid growth.
Invention content
The technical problems to be solved by the invention are to provide a kind of using waste lithium ion cell anode material catalytic degradation
The method of organic wastewater, the present invention carry out at normal temperatures and pressures, and reaction condition is mild, reaction speed is fast, easily operated, catalyst
It is repeatable to utilize.In Disposal of Electronic Wastes and organic wastewater field is administered with very big application potential.
Technical scheme of the present invention is specifically described as follows.
The present invention provide a kind of method using waste lithium ion cell anode material catalytic degradation organic wastewater, including with
Lower step:
(1)Waste and old lithium ion battery is disassembled, takes out positive electrode, after Overheating Treatment, collection cut size size is 10 ~ 100µM positive electrode powder;
(2)Positive electrode powder is placed in progress room temperature absorption in organic wastewater solution, adsorption time is 0.5 ~ 1h, is added in later
Oxidant carries out catalytic degradation under room temperature to organic wastewater;Wherein:The oxidant be selected from sulphite, bisulfites or
One or more of single persulfate PMS.
Above-mentioned steps(1)In, waste and old lithium ion battery is cobalt acid lithium battery or ferric phosphate lithium cell.
Above-mentioned steps(2)In, containing rhodamine, methylene blue or 2 in organic wastewater solution, one kind in 4,6- trichlorophenols
It is or several.
Above-mentioned steps(2)In, the initial pH value of organic wastewater solution is between 2 ~ 9;Organic matter in organic wastewater solution
Total molar concentration between 0.01 mM ~ 1mM.
Above-mentioned steps(1)In, the mass ratio that feeds intake of total organic matter is 1 in positive electrode powder and organic wastewater:10 ~
1:100;Adsorption time is 0.5 ~ 1h.
Above-mentioned steps(2)In, the molar ratio of total organic matter is 2 in oxidant and organic wastewater:1 ~ 100:1.It is preferred that
, molar ratio 20:1~80:1.
Above-mentioned steps(2)In, the degradation reaction time is 1 ~ 30min.
Above-mentioned steps(2)In, the degradation reaction time is 1 ~ 20min.
Compared to the prior art, the invention has the advantages that:
1. the present invention has achieved the purpose that the treatment of wastes with processes of wastes against one another by the use of waste and old lithium ion battery as catalyst degradation organic wastewater.
2. reaction condition of the present invention is mild, reaction speed is fast, and reaction pH ranges are wide, easy to operate.
3. the recyclable recycling of catalyst of the present invention, environmentally protective.
4. degradable organic pollutant of the present invention works well, there is very big application potential in field of environmental improvement.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, those skilled in the art after the content of the invention lectured is read
Various changes or modification can be made to the present invention, such equivalent forms equally fall within what the application the appended claims were limited
Range.
Embodiment 1
The waste and old cobalt acid lithium battery positive electrode rhodamine B degradation of this example(RhB)Method, include the following steps:
1. disassembling cobalt acid lithium battery, the cobalt acid lithium old and useless battery positive electrode powder after Overheating Treatment is collected(Average grain diameter,
10μm).
2. taking three reaction vessels, the RhB solution of 0.01 mmol/L is respectively added thereto.It is 3 to adjust initial pH.
3. the positive electrode powder of 0.12 g/L is respectively put into No. 1 and No. 3 reaction vessels, start timing absorption 1h.
4. taking two groups of certain density sodium hydrogensulfite storing solutions later, it is respectively put into No. 2 and No. 3 reaction vessels, makes
The concentration of sodium hydrogensulfite reaches 1mmol/L, starts degradation reaction.
5. general 30min substantially completely reacts later, the results are shown in Table 1.
1 waste and old cobalt acid lithium battery positive electrode rhodamine B degradation of table
Project | Reaction vessel(No. 1) | Reaction vessel(No. 2) | Reaction vessel(No. 3) |
Additive | Cobalt acid lithium | Sodium hydrogensulfite | Cobalt acid lithium+sodium hydrogensulfite |
RhB degradation rates % | 5.1 | 5.9 | 99.8 |
The result shows that:Individual cobalt acid lithium is put into after RhB solution only 5.1% degradation;Individual solution of sodium bisulfite
It is put into after RhB solution only 5.9% degradation;And combine cobalt acid lithium and sodium hydrogensulfite use, the degradation rate of RhB is reached
To 99.8%.Illustrate that cobalt acid lithium can activate sodium hydrogensulfite, RhB is made to fade rapidly, treatment effect is substantially better than cobalt acid lithium
Or sodium hydrogensulfite independent role.
Embodiment 2
This example positive material of waste lithium iron phosphate degradation of methylene blue(MB)Method, include the following steps:
1. disassemble ferric phosphate lithium cell, collect after Overheating Treatment in LiFePO4 old and useless battery positive electrode powder(It is average
Grain size, 10μm).
2. taking three reaction vessels, 0.03 mmol/LMB solution is respectively added thereto.It is 7 to adjust initial pH.
3. the positive electrode powder of 0.12 g/L is put into No. 1 and No. 3 reaction vessels, starts timing and adsorb 30 min.
4. taking certain density PMS storing solutions later, it is put into No. 2 and No. 3 reaction vessels, reaches the concentration of PMS
1mM starts degradation reaction.
5. substantially completely being reacted after 5 min, the results are shown in Table 2.
The positive material of waste lithium iron phosphate degradation of methylene blue of table 2
Project | Reaction vessel(No. 1) | Reaction vessel(No. 2) | Reaction vessel(No. 3) |
Additive | LiFePO4 | PMS | LiFePO4+PMS |
MB degradation rates % | 4.5 | 20.5 | 99.9 |
The result shows that:Individual LiFePO4 is put into the degradation that MB solution only has 4.5%;It is molten that individual PMS solution is put into MB
Liquid only has 20.5% degradation;And combine LiFePO4 and PMS uses, the degradation rate of MB reaches 99.9%.Illustrate ferric phosphate
Lithium can activate PMS, and MB is made to fade rapidly, and treatment effect is substantially better than LiFePO4 or PMS independent roles.
Embodiment 3
This example waste and old cobalt acid lithium battery positive electrode degradation 2,4,6- trichlorophenols(2,4,6-TCP)Method, including following
Step:
1. disassembling cobalt acid lithium battery, the cobalt acid lithium old and useless battery positive electrode powder after Overheating Treatment is collected(Average grain diameter,
10μm).
2. taking three reaction vessels, 2,4, the 6-TCP solution of 0.05 mM are respectively added thereto.It is 8 to adjust initial pH.
3. the positive electrode powder of 0.12 g/L is put into No. 1 and No. 3 reaction vessels, start timing 1h.
4. taking certain density PMS storing solutions later, it is put into No. 2 and No. 3 reaction vessels, reaches the concentration of PMS
1mM starts degradation reaction.
5. substantially completely being reacted after 20 min, the results are shown in Table 3.
The waste and old cobalt acid lithium battery positive electrode degradation 2,4,6- trichlorophenols of table 3
Project | Reaction vessel(No. 1) | Reaction vessel(No. 2) | Reaction vessel(No. 3) |
Additive | Cobalt acid lithium | PMS | Cobalt acid lithium+PMS |
2,4,6-TCP degradation rates % | 1.7 | 29.3 | 99.9 |
The result shows that:Individual cobalt acid lithium is put into after 2,4,6-TCP solution only 1.7% degradation;Individual PMS is put into
There was only 29.3% degradation after 2,4,6-TCP solution;And combine cobalt acid lithium and PMS uses, to 2,4,6-TCP degradation rate
Reach 99.9%.Illustrate that cobalt acid lithium can activate PMS, make 2,4,6-TCP to degrade rapidly, treatment effect is substantially better than cobalt acid lithium
Or PMS independent roles.
Claims (9)
- A kind of 1. method using waste lithium ion cell anode material catalytic degradation organic wastewater, which is characterized in that including with Lower step:(1)Waste and old lithium ion battery is disassembled, takes out positive electrode, after Overheating Treatment, collection cut size size is 10 ~ 100µThe positive electrode powder of m;(2)Positive electrode powder is poured into the organic wastewater solution being placed on magnetic stirring apparatus and be stirred absorption, during absorption Between for 0.5 ~ 1h, add in oxidant later, catalytic degradation carried out to organic wastewater under room temperature;Wherein:The oxidant is selected from Asia One or more of sulfate, bisulfites or single persulfate PMS.
- 2. according to the method described in claim 1, it is characterized in that:Step(1)In, waste and old lithium ion battery is cobalt acid lithium battery Or ferric phosphate lithium cell.
- 3. according to the method described in claim 1, it is characterized in that, step(2)In, in organic wastewater solution containing rhodamine, One or more of methylene blue or 2,4,6- trichlorophenols.
- 4. according to the method described in claim 1, it is characterized in that, step(2)In, the initial pH value of organic wastewater solution 2 ~ Between 9;Total molar concentration of organic matter in organic wastewater solution is between the mmol/L of 0.01 mmol/L ~ 1.
- 5. according to the method described in claim 1, it is characterized in that, step(1)In, it is total in positive electrode powder and organic wastewater Organic matter the mass ratio that feeds intake for 1:10 ~ 1:100;Adsorption time is 0.5 ~ 1h.
- 6. according to the method described in claim 1, it is characterized in that, step(2)In, it is total organic in oxidant and organic wastewater The molar ratio of object is 2:1 ~ 100:1 .
- 7. according to the method described in claim 1, it is characterized in that, step(2)In, it is total organic in oxidant and organic wastewater The molar ratio of object is 20:1~80:1.
- 8. according to the method described in claim 1, it is characterized in that, step(2)In, the degradation reaction time is 1 ~ 30min.
- 9. according to the method described in claim 1, it is characterized in that, step(2)In, the degradation reaction time is 1 ~ 20min.
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Cited By (6)
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---|---|---|---|---|
CN109244498A (en) * | 2018-09-19 | 2019-01-18 | 上海电力学院 | A kind of recycling and reusing method of waste and old lithium ion battery |
CN110590034A (en) * | 2019-03-12 | 2019-12-20 | 湖北朗润环保科技有限公司 | Process treatment method for lithium iron wastewater of lithium battery anode material |
CN111530466A (en) * | 2020-05-11 | 2020-08-14 | 湖南大学 | Method for removing antibiotics in water body by using catalyst activated permonosulfate prepared from waste lithium batteries |
CN111905720A (en) * | 2020-08-17 | 2020-11-10 | 中国环境科学研究院 | Application of waste battery anode material in catalyst, catalyst and preparation method thereof |
CN113979529A (en) * | 2021-11-15 | 2022-01-28 | 上海第二工业大学 | Advanced oxidation organic wastewater treatment system and method based on resource utilization of waste lithium iron phosphate material |
CN115999604A (en) * | 2022-12-15 | 2023-04-25 | 广东省科学院生态环境与土壤研究所 | Method for preparing efficient core-shell structure catalyst by taking tail end waste residue recovered from waste ternary lithium battery as raw material, product and application |
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CN109244498A (en) * | 2018-09-19 | 2019-01-18 | 上海电力学院 | A kind of recycling and reusing method of waste and old lithium ion battery |
CN110590034A (en) * | 2019-03-12 | 2019-12-20 | 湖北朗润环保科技有限公司 | Process treatment method for lithium iron wastewater of lithium battery anode material |
CN111530466A (en) * | 2020-05-11 | 2020-08-14 | 湖南大学 | Method for removing antibiotics in water body by using catalyst activated permonosulfate prepared from waste lithium batteries |
WO2021227213A1 (en) * | 2020-05-11 | 2021-11-18 | 湖南大学 | Catalyst for use in removing antibiotics in water body by activating peroxymonosulfate, preparation method therefor, and application thereof |
CN111905720A (en) * | 2020-08-17 | 2020-11-10 | 中国环境科学研究院 | Application of waste battery anode material in catalyst, catalyst and preparation method thereof |
CN111905720B (en) * | 2020-08-17 | 2021-08-06 | 中国环境科学研究院 | Application of waste battery anode material in catalyst, catalyst and preparation method thereof |
CN113979529A (en) * | 2021-11-15 | 2022-01-28 | 上海第二工业大学 | Advanced oxidation organic wastewater treatment system and method based on resource utilization of waste lithium iron phosphate material |
CN115999604A (en) * | 2022-12-15 | 2023-04-25 | 广东省科学院生态环境与土壤研究所 | Method for preparing efficient core-shell structure catalyst by taking tail end waste residue recovered from waste ternary lithium battery as raw material, product and application |
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