CN110203949B - Method for fully recycling electrolyte of waste lithium ion battery - Google Patents
Method for fully recycling electrolyte of waste lithium ion battery Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 87
- 239000002699 waste material Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- 238000004064 recycling Methods 0.000 title abstract description 4
- 238000011084 recovery Methods 0.000 claims abstract description 53
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 39
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 39
- 239000003960 organic solvent Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 238000004140 cleaning Methods 0.000 claims abstract description 26
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011737 fluorine Substances 0.000 claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000006259 organic additive Substances 0.000 claims abstract description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims description 54
- 238000001914 filtration Methods 0.000 claims description 40
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 2
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 20
- 239000000654 additive Substances 0.000 description 18
- 229910001634 calcium fluoride Inorganic materials 0.000 description 17
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 16
- 239000001506 calcium phosphate Substances 0.000 description 16
- 229910000389 calcium phosphate Inorganic materials 0.000 description 16
- 235000011010 calcium phosphates Nutrition 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 16
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 16
- 239000008346 aqueous phase Substances 0.000 description 15
- 238000004821 distillation Methods 0.000 description 10
- 238000002791 soaking Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
本发明提供了一种废旧锂离子电池电解液全回收方法，目的是回收废旧电解液中有价值的锂盐、有机溶剂和添加剂，并且对氟、磷等有害杂质进行无害化处理后回收。本发明经过清洗、清洗溶剂回收、有机溶剂和添加剂回收、氟和磷回收、锂盐回收工序，锂盐最终以碳酸锂的形式回收，有机溶剂、添加剂分离提纯回收利用，氟、磷以沉淀的形式回收利用。此工艺简单，方法可行，对废旧电解液进行充分的回收利用且对环境没有污染，利用此工艺回收废旧电解液各组分，回收率达95%以上，适合大规模工业化应用。
The invention provides a method for fully recovering the electrolyte of waste and used lithium ion batteries, which aims to recover valuable lithium salts, organic solvents and additives in waste and used electrolytes, and to recover fluorine, phosphorus and other harmful impurities after harmless treatment. In the present invention, through the steps of cleaning, cleaning solvent recovery, organic solvent and additive recovery, fluorine and phosphorus recovery, and lithium salt recovery, the lithium salt is finally recovered in the form of lithium carbonate, the organic solvent and additives are separated, purified and recycled, and fluorine and phosphorus are precipitated in the form of form recycling. The process is simple, the method is feasible, and the waste electrolyte can be fully recycled without pollution to the environment. Using this process to recover the components of the waste electrolyte, the recovery rate is over 95%, which is suitable for large-scale industrial applications.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a method for completely recovering electrolyte of a waste lithium ion battery.
Background
With the global energy crisis and the aggravation of environmental pollution, the development and application of new energy are imperative. Lithium ion batteries have been rapidly developed since commercialization in the 90 s of the 20 th century. Compared with the traditional chemical battery, the battery has the advantages of light weight, small volume, high voltage, high specific energy, wide working temperature range, high specific power, stable discharge, long storage time, no memory effect, no pollution and the like. At present, lithium ion batteries have been widely used in portable electronic products such as mobile phones, digital cameras, notebook computers, and the like, and have shown wide application prospects in Electric Vehicles (EV), Hybrid Electric Vehicles (HEV), and energy storage systems, and are known as "green secondary batteries in the 21 st century". According to the forecast of the China automobile technology research center, the accumulated scrappage of the power battery of the electric automobile reaches 12-17 ten thousand tons in 2020, and serious environmental pollution is caused if the power battery is not properly treated. At present, the recovery of waste lithium ion batteries is mainly focused on anode and cathode materials and current collectors, and the research on the recovery of electrolyte is few. The electrolyte generally comprises lithium salt, an organic solvent and an additive, wherein the lithium salt is mainly lithium hexafluorophosphate, the organic solvent mainly comprises a carbonate solvent, and the additive content is low. The existence of lithium hexafluorophosphate enables the electrolyte to be in contact with the external environment for reaction, a large amount of pollutants are generated, and important influence is brought to the safety of people and the environmental problem. Meanwhile, the electrolyte has high added value, and how to reasonably recover the electrolyte is a problem worthy of deep research.
The existing recovery methods of lithium ion battery electrolyte comprise an alkali liquor absorption method, a vacuum distillation method and an extraction method. Patent CN 108666644A adopts Ca (OH)2Reaction with spent electrolyte of lithium ion battery, Ca2+React with fluoride ions in the electrolyte to generate CaF2And then, a multi-stage manganese fiber adsorption column and a titanium fiber adsorption column are adopted to carry out physical directional adsorption on lithium ions, so that fluorine and lithium in the electrolyte are recovered, the fluorine and lithium can be recycled, and the environmental pollution can be reduced. Although the method can reduce the pollution of fluorine to the environment and recover lithium resources, the method does not recover the carbonate organic solvent and the additive in the electrolyte and directly adds Ca (OH) into the waste electrolyte2The solution can destroy the organic solvent and the additive, and cause resource waste. Patent CN 109292746A mixes old and useless lithium cell book core with organic solvent, enables the positive negative pole material and the diaphragm of battery and organic solvent fully to contact, then under the ultrasonic action, transfers the lithium hexafluorophosphate that adheres in positive negative pole material, diaphragm and electrolyte to the mixed organic solvent of acetonitrile and carbonic ester, and then realizes that the high efficiency of lithium hexafluorophosphate returnsAnd (6) harvesting. Although the method can effectively recover the lithium hexafluorophosphate, the lithium hexafluorophosphate is unstable and easy to decompose, has high requirements on the breaking-in and enrichment processes, and increases the process cost.
At present, the treatment of the waste lithium ion battery electrolyte in the industry is calcination cracking treatment after heating evaporation, the cracking of an organic solvent needs high-temperature calcination treatment and energy consumption, ethylene carbonate, propylene carbonate, an additive and the like contained in the electrolyte have higher values, and the direct calcination is contrary to the strategy of sustainable development advocated by the state. Therefore, how to efficiently and feasibly recover lithium salt, fluorine and phosphorus in the waste electrolyte for recycling after harmless treatment, and not to damage the structures of the organic solvent and the additive is a difficult problem facing the lithium ion battery industry.
Disclosure of Invention
The invention provides a method for fully recovering waste lithium ion battery electrolyte, lithium salt is finally recovered in the form of lithium carbonate, an organic solvent and an additive are separated, purified and recycled, fluorine and phosphorus are recovered and utilized in the form of precipitates, the process is simple and feasible, the waste electrolyte is fully recovered and utilized, no pollution is caused to the environment, all components of the waste electrolyte are recovered by the process, the recovery rate reaches over 95 percent, and the method is suitable for large-scale industrial application.
The technical scheme for realizing the invention is as follows:
a method for fully recovering electrolyte of a waste lithium ion battery comprises the following steps:
(1) a cleaning procedure: soaking a waste lithium ion battery containing waste electrolyte in a cleaning solvent, and carrying out ultrasonic treatment, stirring and filtering on the waste lithium ion battery;
(2) a cleaning solvent recovery step: carrying out reduced pressure distillation on the filtrate obtained after the filtration in the step (1), and collecting electrolyte;
(3) organic solvent and additive recovery process: adding water into the electrolyte collected in the step (2), heating, filtering to obtain lithium salt precipitate and filtrate, introducing the filtrate into an extraction tower, purifying and separating organic phases one by one through a separation device, and recovering an organic solvent and an additive;
(4) a lithium salt recovery step: and (4) adding the lithium salt precipitate obtained in the step (3) into a calcium hydroxide solution, and filtering to obtain a filtrate I.
The cleaning solvent in the step (1) is one or more of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and propylene carbonate.
The vacuum degree of the reduced pressure distillation in the step (2) is 100-500 mbar, and the temperature is 30-100 ℃.
The heating temperature in the step (3) is 30-100 ℃.
The separation device in the step (3) is a rectifying tower, the number of tower plates of the rectifying tower is 5-80, the reflux ratio is 2-60, the reaction temperature is 50-250 ℃, and the operation pressure is 10-80 KPa.
And (4) absorbing the volatile gas generated by heating in the step (3) by using a calcium hydroxide solution, absorbing the water phase by using the calcium hydroxide solution, recovering fluorine and phosphorus, and filtering to obtain a filtrate II.
And introducing water-soluble carbonate or carbon dioxide into the filtrate I and the filtrate II to generate lithium carbonate to be separated out, wherein the carbonate is one or more of sodium carbonate, potassium carbonate and ammonium carbonate.
The invention has the beneficial effects that: compared with the prior art, the method has the advantages of simple process, high feasibility and no pollution while recovering the lithium salt, the organic solvent, the additive, the fluorine and the phosphorus. The invention plays a positive role in saving resources, protecting environment and realizing sustainable development.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a flow chart of a full recovery process of waste lithium ion battery electrolyte.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A method for fully recovering electrolyte of a waste lithium ion battery comprises the following steps:
(1) cleaning process
Soaking a waste lithium ion battery containing waste electrolyte in a dimethyl carbonate solvent, and extracting the electrolyte after performing ultrasonic treatment, stirring and filtering on the waste lithium ion battery;
(2) cleaning solvent recovery step
Controlling the vacuum degree to be 100mbar and the temperature to be 30 ℃ to carry out reduced pressure distillation, recovering the dimethyl carbonate solvent used in the working procedure (1), and collecting the electrolyte;
(3) organic solvent and additive recovery step
Adding water into the collected electrolyte in the step (2), heating at 30 ℃, filtering to obtain lithium salt precipitate and filtrate, introducing the filtrate into an extraction tower, purifying and separating organic phases one by one through a rectifying tower, wherein the number of tower plates of the rectifying tower is 40, the reaction temperature is 150 ℃, the operating pressure is 20KPa, the reflux ratio is 5, and recovering an organic solvent and an additive;
(4) recovery process of fluorine and phosphorus in electrolyte
Absorbing the volatile gas generated by heating in the step (3) by using a calcium hydroxide solution, and absorbing the aqueous phase in the step (3) by using the calcium hydroxide solution to generate calcium fluoride and calcium phosphate and then recovering the calcium fluoride and the calcium phosphate;
(5) lithium salt recovery step
Adding the lithium salt precipitate obtained in the step (3) into a calcium hydroxide solution, filtering to obtain a filtrate I, reacting the aqueous phase with the calcium hydroxide solution in the step (4), filtering to obtain a filtrate II, putting the obtained filtrates I and II into a crystallization kettle, adding a sodium carbonate solution into the crystallization kettle, heating, concentrating and crystallizing to generate lithium carbonate.
Example 2
A method for fully recovering electrolyte of a waste lithium ion battery comprises the following steps:
(1) cleaning process
Soaking a waste lithium ion battery containing waste electrolyte in a methyl ethyl carbonate solvent, and extracting the electrolyte after performing ultrasonic treatment, stirring and filtering on the waste lithium ion battery;
(2) cleaning solvent recovery step
Controlling the vacuum degree to be 500mbar and the temperature to be 100 ℃, carrying out reduced pressure distillation, recovering the methyl ethyl carbonate solvent used in the working procedure (1), and collecting the electrolyte;
(3) organic solvent and additive recovery step
Adding water into the collected electrolyte in the step (2), heating at 100 ℃, filtering to obtain lithium salt precipitate and filtrate, introducing the filtrate into an extraction tower, purifying and separating organic phases one by one through a rectifying tower, wherein the number of tower plates of the rectifying tower is 80, the reaction temperature is 250 ℃, the operating pressure is 80KPa, the reflux ratio is 60, and recovering an organic solvent and an additive;
(4) recovery process of fluorine and phosphorus in electrolyte
Absorbing the volatile gas generated by heating in the step (3) by using a calcium hydroxide solution, and absorbing the aqueous phase in the step (3) by using the calcium hydroxide solution to generate calcium fluoride and calcium phosphate and then recovering the calcium fluoride and the calcium phosphate;
(5) lithium salt recovery step
And (3) adding the lithium salt precipitate in the step (3) into a calcium hydroxide solution, filtering to obtain a filtrate I, reacting the aqueous phase with the calcium hydroxide solution in the step (4), filtering to obtain a filtrate II, putting the obtained filtrates I and II into a crystallization kettle, adding a potassium carbonate solution into the crystallization kettle, heating, concentrating and crystallizing to generate lithium carbonate.
Example 3
A method for fully recovering electrolyte of a waste lithium ion battery comprises the following steps:
(1) cleaning process
Soaking a waste lithium ion battery containing waste electrolyte in a diethyl carbonate solvent, and extracting the electrolyte after performing ultrasonic treatment, stirring and filtering on the waste lithium ion battery;
(2) cleaning solvent recovery step
Controlling the vacuum degree to be 200mbar and the temperature to be 50 ℃ to carry out reduced pressure distillation, recovering the diethyl carbonate solvent used in the working procedure (1), and collecting the electrolyte;
(3) organic solvent and additive recovery step
Adding water into the collected electrolyte in the step (2), heating at 50 ℃, filtering to obtain lithium salt precipitate and filtrate, introducing the filtrate into an extraction tower, purifying and separating organic phases one by one through a rectifying tower, wherein the number of tower plates of the rectifying tower is 5, the reaction temperature is 50 ℃, the operating pressure is 10KPa, the reflux ratio is 2, and recovering an organic solvent and an additive;
(4) recovery process of fluorine and phosphorus in electrolyte
Absorbing the volatile gas generated by heating in the step (3) by using a calcium hydroxide solution, and absorbing the aqueous phase in the step (3) by using the calcium hydroxide solution to generate calcium fluoride and calcium phosphate and then recovering the calcium fluoride and the calcium phosphate;
(5) lithium salt recovery step
And (3) adding the lithium salt precipitate in the step (3) into a calcium hydroxide solution, filtering to obtain a filtrate I, reacting the aqueous phase with the calcium hydroxide solution in the step (4), filtering to obtain a filtrate II, putting the obtained filtrates I and II into a crystallization kettle, adding an ammonium carbonate solution into the crystallization kettle, heating, concentrating and crystallizing to generate lithium carbonate.
Example 4
A method for fully recovering electrolyte of a waste lithium ion battery comprises the following steps:
(1) cleaning process
The method comprises the steps of soaking a waste lithium ion battery containing waste electrolyte in a propylene carbonate solvent, and extracting the electrolyte after carrying out ultrasonic treatment, stirring and filtering on the waste lithium ion battery.
(2) Cleaning solvent recovery step
Controlling the vacuum degree to be 400mbar and the temperature to be 80 ℃ to carry out reduced pressure distillation, recovering the propylene carbonate solvent used in the working procedure (1), and collecting the electrolyte;
(3) organic solvent and additive recovery step
Adding water into the collected electrolyte in the step (2), heating at 60 ℃, filtering to obtain lithium salt precipitate and filtrate, introducing the filtrate into an extraction tower, purifying and separating organic phases one by one through a rectifying tower, wherein the number of tower plates of the rectifying tower is 20, the reaction temperature is 100 ℃, the operating pressure is 30KPa, the reflux ratio is 20, and recovering an organic solvent and an additive;
(4) recovery process of fluorine and phosphorus in electrolyte
Absorbing the volatile gas generated by heating in the step (3) by using a calcium hydroxide solution, and absorbing the aqueous phase in the step (3) by using the calcium hydroxide solution to generate calcium fluoride and calcium phosphate and then recovering the calcium fluoride and the calcium phosphate;
(5) lithium salt recovery step
And (3) adding the lithium salt precipitate in the step (3) into a calcium hydroxide solution, filtering to obtain a filtrate I, reacting the aqueous phase with the calcium hydroxide solution in the step (4), filtering to obtain a filtrate II, putting the obtained filtrates I and II into a crystallization kettle, introducing carbon dioxide gas into the crystallization kettle, heating, concentrating and crystallizing to generate lithium carbonate.
Example 5
A method for fully recovering electrolyte of a waste lithium ion battery comprises the following steps:
(1) cleaning process
Soaking a waste lithium ion battery containing waste electrolyte in a methyl ethyl carbonate solvent, and extracting the electrolyte after performing ultrasonic treatment, stirring and filtering on the waste lithium ion battery;
(2) cleaning solvent recovery step
Controlling the vacuum degree to be 300mbar and the temperature to be 60 ℃ to carry out reduced pressure distillation, recovering the methyl ethyl carbonate solvent used in the working procedure (1), and collecting the electrolyte;
(3) organic solvent and additive recovery step
Adding water into the collected electrolyte in the step (2), heating at 50 ℃, filtering to obtain lithium salt precipitate and filtrate, introducing the filtrate into an extraction tower, purifying and separating organic phases one by one through a rectifying tower, wherein the number of tower plates of the rectifying tower is 30, the reaction temperature is 150 ℃, the operating pressure is 40KPa, the reflux ratio is 30, and recovering an organic solvent and an additive;
(4) recovery process of fluorine and phosphorus in electrolyte
Absorbing the volatile gas generated by heating in the step (3) by using a calcium hydroxide solution, and absorbing the aqueous phase in the step (3) by using the calcium hydroxide solution to generate calcium fluoride and calcium phosphate and then recovering the calcium fluoride and the calcium phosphate;
(5) lithium salt recovery step
And (3) adding acetic acid into the lithium salt precipitate in the step (3) to form a filtrate, separating and removing the precipitate formed in the step (4) to obtain a filtrate, putting the obtained filtrate into a crystallization kettle, introducing carbon dioxide gas into the crystallization kettle, heating, concentrating and crystallizing to obtain the lithium carbonate.
Example 6
A method for fully recovering electrolyte of a waste lithium ion battery comprises the following steps:
(1) cleaning process
Soaking a waste lithium ion battery containing waste electrolyte in a dimethyl carbonate solvent, and extracting the electrolyte after performing ultrasonic treatment, stirring and filtering on the waste lithium ion battery;
(2) cleaning solvent recovery step
Controlling the vacuum degree to be 400mbar and the temperature to be 80 ℃ to carry out reduced pressure distillation, recovering the dimethyl carbonate solvent used in the working procedure (1), and collecting the electrolyte;
(3) organic solvent and additive recovery step
Adding water into the collected electrolyte in the step (2), heating at 70 ℃, filtering to obtain lithium salt precipitate and filtrate, introducing the filtrate into an extraction tower, purifying and separating organic phases one by one through a rectifying tower, wherein the number of tower plates of the rectifying tower is 40, the reaction temperature is 180 ℃, the operating pressure is 50KPa, the reflux ratio is 40, and recovering an organic solvent and an additive;
(4) recovery process of fluorine and phosphorus in electrolyte
Absorbing the volatile gas generated by heating in the step (3) by using a calcium hydroxide solution, and absorbing the aqueous phase in the step (3) by using the calcium hydroxide solution to generate calcium fluoride and calcium phosphate and then recovering the calcium fluoride and the calcium phosphate;
(5) lithium salt recovery step
And (3) adding the lithium salt precipitate in the step (3) into a calcium hydroxide solution, filtering to obtain a filtrate I, reacting the aqueous phase with the calcium hydroxide solution in the step (4), filtering to obtain a filtrate II, putting the obtained filtrates I and II into a crystallization kettle, adding a potassium carbonate solution into the crystallization kettle, heating, concentrating and crystallizing to generate lithium carbonate.
Example 7
A method for fully recovering electrolyte of a waste lithium ion battery comprises the following steps:
(1) cleaning process
Soaking a waste lithium ion battery containing waste electrolyte in a propylene carbonate solvent, and extracting the electrolyte after performing ultrasonic treatment, stirring and filtering on the waste lithium ion battery;
(2) cleaning solvent recovery step
Controlling the vacuum degree to be 200mbar and the temperature to be 50 ℃ to carry out reduced pressure distillation, recovering the propylene carbonate solvent used in the working procedure (1), and collecting the electrolyte;
(3) organic solvent and additive recovery step
Adding excessive water into the collected electrolyte in the step (2), heating at 80 ℃, filtering to obtain lithium salt precipitate and filtrate, introducing the filtrate into an extraction tower, purifying and separating the organic phase one by one through a rectifying tower, wherein the tower plate number of the rectifying tower is 80, the reaction temperature is 220 ℃, the operating pressure is 60KPa, the reflux ratio is 50, and recovering the organic solvent and the additive;
(4) recovery process of fluorine and phosphorus in electrolyte
Absorbing the volatile gas generated by heating in the step (3) by using a calcium hydroxide solution, and absorbing the aqueous phase in the step (3) by using the calcium hydroxide solution to generate calcium fluoride and calcium phosphate and then recovering the calcium fluoride and the calcium phosphate;
(5) lithium salt recovery step
Adding the lithium salt precipitate obtained in the step (3) into a calcium hydroxide solution, filtering to obtain a filtrate I, reacting the aqueous phase with the calcium hydroxide solution in the step (4), filtering to obtain a filtrate II, putting the obtained filtrates I and II into a crystallization kettle, adding a sodium carbonate solution into the crystallization kettle, heating, concentrating and crystallizing to generate lithium carbonate.
Example 8
A method for fully recovering electrolyte of a waste lithium ion battery comprises the following steps:
(1) cleaning process
Soaking a waste lithium ion battery containing waste electrolyte in a diethyl carbonate solvent, and extracting the electrolyte after performing ultrasonic treatment, stirring and filtering on the waste lithium ion battery;
(2) cleaning solvent recovery step
Controlling the vacuum degree to be 100mbar and the temperature to be 40 ℃ to carry out reduced pressure distillation, recovering the diethyl carbonate solvent used in the step (1), and collecting the electrolyte;
(3) organic solvent and additive recovery step
Adding water into the collected electrolyte in the step (2), heating at 40 ℃, filtering to obtain lithium salt precipitate and filtrate, introducing the filtrate into an extraction tower, purifying and separating organic phases one by one through a rectifying tower, wherein the number of tower plates of the rectifying tower is 50, the reaction temperature is 240 ℃, the operating pressure is 60KPa, the reflux ratio is 15, and recovering an organic solvent and an additive;
(4) recovery process of fluorine and phosphorus in electrolyte
Absorbing the volatile gas generated by heating in the step (3) by using a calcium hydroxide solution, and absorbing the aqueous phase in the step (3) by using the calcium hydroxide solution to generate calcium fluoride and calcium phosphate and then recovering the calcium fluoride and the calcium phosphate;
(5) lithium salt recovery step
And (3) adding the lithium salt precipitate in the step (3) into a calcium hydroxide solution, filtering to obtain a filtrate I, reacting the aqueous phase with the calcium hydroxide solution in the step (4), filtering to obtain a filtrate II, putting the obtained filtrates I and II into a crystallization kettle, introducing carbon dioxide gas into the crystallization kettle, heating, concentrating and crystallizing to generate lithium carbonate.
TABLE 1 recovery of various components of spent electrolyte
Verification of effects
Table 1 shows the recovery rates of the components of the spent electrolyte in the examples.
Fig. 1 is a process flow diagram for the total recovery of the electrolyte of the waste lithium ion battery, and the effective recovery of lithium salt, organic solvent, additive, fluorine and phosphorus can be clearly seen from the diagram.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
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| CN110635191A (en) * | 2019-09-12 | 2019-12-31 | 金川集团股份有限公司 | Method for cleanly recovering all components of waste power lithium battery |
| CN111003736B (en) * | 2019-11-08 | 2022-10-04 | 惠州亿纬锂能股份有限公司 | Comprehensive treatment method for lithium ion battery electrolyte |
| CN111678838A (en) * | 2020-05-20 | 2020-09-18 | 超威电源集团有限公司 | Device for collecting electrolyte in AGM separator and method for obtaining electrolyte density |
| CN111924816A (en) * | 2020-07-02 | 2020-11-13 | 曲靖市华祥科技有限公司 | Method for recovering electrolyte of waste lithium ion battery |
| CN112408437B (en) * | 2020-11-19 | 2023-03-28 | 江西天新药业股份有限公司 | Method for recovering lithium salt |
| CN112421143A (en) * | 2020-11-30 | 2021-02-26 | 湖南金源新材料股份有限公司 | Comprehensive recovery method of waste lithium battery electrolyte |
| CN113363610B (en) * | 2021-06-18 | 2022-11-22 | 郑州中科新兴产业技术研究院 | A kind of harmless treatment method of decommissioned lithium-ion battery electrolyte |
| CN113471515A (en) * | 2021-06-30 | 2021-10-01 | 广州市浩立生物科技有限公司 | Method for recycling lithium battery electrolyte by combining supercritical extraction rectification and molecular distillation |
| CN114039116B (en) * | 2021-08-30 | 2024-12-17 | 雅邦绿色过程与新材料研究院南京有限公司 | Comprehensive recovery and regeneration method for lithium ion battery waste electrolyte |
| CN114524548B (en) * | 2022-03-07 | 2024-12-03 | 安徽浩悦环境科技股份有限公司 | Treatment method and treatment system for lithium battery electrolyte waste |
| CN114804162B (en) * | 2022-04-14 | 2024-01-16 | 江西理工大学 | Low-temperature recovery method for lithium ion battery electrolyte |
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