CN116835613A - LiBF (LiBF) treated by high-frequency electromagnetic waves 4 Method for preparing condensed electrolyte and by-producing lithium chloride and calcium borate - Google Patents
LiBF (LiBF) treated by high-frequency electromagnetic waves 4 Method for preparing condensed electrolyte and by-producing lithium chloride and calcium borate Download PDFInfo
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- CN116835613A CN116835613A CN202310703715.2A CN202310703715A CN116835613A CN 116835613 A CN116835613 A CN 116835613A CN 202310703715 A CN202310703715 A CN 202310703715A CN 116835613 A CN116835613 A CN 116835613A
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- calcium borate
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 title claims abstract description 60
- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910013075 LiBF Inorganic materials 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 31
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052796 boron Inorganic materials 0.000 claims abstract description 20
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 17
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims abstract description 16
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 16
- 239000001110 calcium chloride Substances 0.000 claims abstract description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 239000004571 lime Substances 0.000 claims abstract description 6
- 238000001728 nano-filtration Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 47
- 239000000706 filtrate Substances 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 16
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 9
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 5
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 5
- 229920006218 cellulose propionate Polymers 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 5
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- YYPAYCHEKJAQAK-UHFFFAOYSA-N C=CC.F Chemical group C=CC.F YYPAYCHEKJAQAK-UHFFFAOYSA-N 0.000 claims description 3
- 229920008347 Cellulose acetate propionate Polymers 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 231100000331 toxic Toxicity 0.000 claims description 3
- 230000002588 toxic effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000012459 cleaning agent Substances 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000004880 explosion Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/126—Borates of alkaline-earth metals, beryllium, aluminium or magnesium
-
- 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
- C01F11/24—Chlorides
- C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
The application relates to the field of lithium ion battery resource utilization, in particular to a method for processing LiBF by high-frequency electromagnetic waves 4 The method for condensing electrolyte and by-producing lithium chloride and calcium borate comprises the following steps: washing LiBF with 70-75 deg.C ethanol 4 An organic solvent and a lithium salt in the condensed electrolyte; adding an aluminum chloride solution into the ethanol cleaning agent, converting fluorine into aluminum fluoride precipitate, and performing air floatation treatment to obtain an organic solvent I; adding a certain amount of lime into the solution after air floatation, and converting boron element into calcium borate for precipitation; re-pairingRectifying the solution to recover ethanol solvent; and (3) recovering the organic solvent II from the rectified solution by using an adsorption resin, sequentially performing resin boron removal, nanofiltration, evaporation and drying treatment, and respectively obtaining solid lithium chloride and solid calcium chloride.
Description
Technical Field
The application relates to the field of lithium ion battery resource utilization, in particular to a method for processing LiBF by high-frequency electromagnetic waves 4 A method for condensing electrolyte and by-producing lithium chloride and calcium borate.
Background
The continuous shortage of fossil resources and the increasing increase in environmental pollution have led to the increasing popularity of green, efficient, clean electric vehicles. In order to realize large-scale popularization of electric automobiles, improving the energy density of a power battery has become the most important research direction in the world at present. The energy density of the battery is improved, the endurance mileage can be increased, the cost of the battery core can be reduced, and the service life can be prolonged. However, as the energy density of the secondary battery increases, the energy released by the explosion of the battery increases, and the resulting hazard is more serious. In recent years, fire and explosion accidents caused by power batteries are frequent, and the safety problem of secondary batteries causes resonance of people. At present, the secondary battery mainly uses liquid electrolyte, but the secondary battery using the liquid electrolyte still has potential safety hazards such as internal short circuit, liquid leakage, combustion, explosion and the like. When the battery is subjected to conditions of overcharge, discharge, impact, puncture and the like, the battery is extremely easy to cause explosion accidents.
Therefore, solid-state batteries, semi-solid batteries, and condensed batteries, which are highly safe and have good cycle performance, are receiving a great deal of attention, and particularly, condensed batteries are most prominent. The core of the condensed state battery is condensed state electrolyte, which can realize super-fluidization state and super-conduction state, and has more excellent stability and conductivity. For example, chinese patent publication No. CN105845978A discloses a lithium ion battery, which uses a silicon-based negative electrode and a polymer electrolyte, wherein the polymer electrolyte includes a nonaqueous organic solvent, a lithium salt, an additive and a polymer (a carboxylic acid cellulose, a fluoroolefin polymer) dispersed in the electrolyte, and the polymer electrolyte can be converted into a gel electrolyte (i.e., a condensed electrolyte) having both excellent mechanical stability and ion transport property after being formed at a high temperature. Remarks: the carboxylic acid cellulose is selected from one or a combination of more of cellulose acetate propionate, cellulose acetate butyrate and cellulose propionate butyrate; the fluorine-containing olefin polymer is selected from one or a combination of more of polyvinylidene fluoride, polyvinylidene fluoride propylene, and copolymer of vinylidene fluoride and hexafluoropropylene.
When the condensed battery reaches the service life, the condensed battery needs to be recycled, and the recycling of the condensed battery has the difficulty that the core of the condensed battery is one-to-one recycling of condensed electrolyte. The structure of the condensed electrolyte is different from that of the traditional liquid electrolyte, and the organic solvent (containing the additive) and the lithium salt are solidified and bound by the polymer in a gel form and cannot flow freely, so that the organic solvent (containing the additive), the lithium salt and the polymer are difficult to separate and recycle independently; second, due to lithium salt LiBF 4 Highly toxic hydrogen fluoride gas is easily generated by hydrolysis after meeting water, so that the conventional wet recycling process has a certain safety risk; if the fire recovery process is adopted, not only organic solvents and polymers are lost, but also a large amount of waste gas pollutants are generated.
Disclosure of Invention
The purpose of the application is that: provides a LiBF 4 The recovery method of the condensed electrolyte does not produce any waste pollutants while separately recovering lithium salt, organic solvent (including additives) and polymer.
The technical scheme of the application is as follows:
(1) Discharging and disassembling the waste condensed lithium ion battery, and taking out LiBF 4 An electrolyte in a condensed state.
(2) The LiBF is prepared by 4 Soaking the condensed electrolyte in an ethanol solvent with the volume of 2.5-3 times, continuously stirring for 8-10 hours at the temperature of 70-75 ℃ under the pressure of 1.2-1.4 Bar, and then separating the organic solvent, the additive and the lithium salt which are solidified and bound in the polymer from the polymer into the ethanol solvent, and carrying out solid-liquid separation on the solid solvent by a filter press to obtain a solid polymer (carboxylic cellulose and fluorine-containing olefin polymer) and ethanol leaching solution; the solid polymer can be reused for the production of the condensed electrolyte after being washed by ethanol for the second time.
(3) Adding an aluminum chloride solution into the ethanol leaching solution according to the volume ratio of the aluminum chloride solution to the ethanol solvent of 1:1, heating the solution to 90 ℃ by using high-frequency electromagnetic waves with the frequency of 915MHz, stirring and reacting for 70-80 min, thoroughly converting fluorine element in the solution into aluminum fluoride under the catalysis of the electromagnetic waves, carrying out solid-liquid separation to obtain aluminum fluoride precipitate and filtrate I, and carrying out air floatation treatment on the filtrate I to obtain an organic solvent I and filtrate II.
(4) And adding a certain amount of lime into the filtrate II, regulating the pH value of the solution to 7.0-7.2, stirring and reacting for 10min, and then carrying out solid-liquid separation to obtain solid precipitated calcium borate and filtrate III.
(5) Rectifying the filtrate III, and separating out an ethanol solvent to obtain a mixed solution I; the ethanol solvent is reused for the treatment of the LiBF4 condensed electrolyte.
(6) And (3) separating the organic matters in the mixed solution I by using an adsorption resin to obtain a mixed solution II, and removing the resin to obtain an organic solvent II.
(7) Separating boron element in the mixed solution II by using boron adsorption resin to obtain a mixed solution III; and (3) after the boron adsorption resin is saturated, desorbing by using a 1mol/L sodium hydroxide solution to obtain a sodium borate solution.
(8) Carrying out nanofiltration treatment on the mixed solution III to obtain lithium chloride filtrate and calcium chloride concentrate; evaporating and drying the lithium chloride solution and the calcium chloride solution respectively to obtain solid lithium chloride and solid calcium chloride.
Wherein: the carboxylic acid cellulose is one or a combination of more of cellulose acetate propionate, cellulose acetate butyrate and cellulose propionate butyrate.
Wherein: the fluorine-containing olefin polymer is one or the combination of more of polyvinylidene fluoride, polyvinylidene fluoride propylene, and copolymer of vinylidene fluoride and hexafluoropropylene.
Wherein: adding aluminum chloride according to the mole ratio of Al to F of 1 to 3, which has the function of converting fluorine element into stable aluminum fluoride precipitate and preventing LiBF 4 Hydrolysis produces highly toxic hydrogen fluoride, and aluminum fluoride can be sold as a product for aluminum production.
Wherein: 3LiBF 4 +4AlCl 3 +9H 2 O＝9HCl+3LiCl+3H 3 BO 3 +4AlF 3 And ∈s a reaction equation for generating aluminum fluoride.
Wherein: the organic solvent I is one or the combination of a plurality of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and fluoroethylene carbonate.
Wherein: the organic solvent II is one or the combination of more of ethylene carbonate, propylene carbonate and propane sultone.
Wherein: the organic solvent I and the organic solvent II can be reused for the production of the condensed electrolyte.
Wherein: the boron element in the electrolyte is recovered in the form of calcium borate, and the calcium borate can be used as a product in the ceramic industry.
The beneficial effects of the application are as follows: the gel-cured organic solvent (containing additives), lithium salt and polymer can be effectively separated and recycled independently; the recovered organic solvent (containing additives) and polymer can be reused for preparing the condensed electrolyte; recovering lithium element in the form of solid lithium chloride; the generation of hydrogen fluoride is inhibited in the form of aluminum fluoride, and fluorine element is recovered, so that the aluminum fluoride can be used for aluminum smelting production; the boron element is recovered in the form of calcium borate, and can be used as a product to be applied to the ceramic industry; calcium chloride can also be sold as a product; the whole process is green and environment-friendly, and no waste pollutant is generated.
Detailed Description
The present application will be described more fully hereinafter with reference to the preferred embodiments, but not limiting to the application.
Example 1
LiBF 4 The components of the condensed electrolyte are as follows: taking a mixture of cellulose acetate butyrate (70000) and vinylidene fluoride and hexafluoropropylene copolymer (80000) =7:3 as a polymer; ethylene carbonate, propylene carbonate and diethyl carbonate are used as organic solvents; fluoroethylene carbonate and propane sultone are used as additives; liBF 4 And (3) preparing lithium salt.
(1) Discharging and disassembling the waste condensed lithium ion battery, and taking out LiBF 4 An electrolyte in a condensed state.
(2) The LiBF is prepared by 4 Soaking the condensed electrolyte in an ethanol solvent with the volume of 2.8 times, continuously stirring for 9 hours at 73 ℃ and 1.4Bar, and then carrying out solid-liquid separation on the electrolyte by using a filter press to obtain a solid polymer (cellulose acetate butyrate, copolymer of vinylidene fluoride and hexafluoropropylene) and ethanol leaching solution; the solid polymer can be reused for the production of the condensed electrolyte after being washed by ethanol for the second time.
(3) Adding an aluminum chloride solution into the ethanol leaching solution according to the mole ratio of Al to F of 1:3 and the volume ratio of the aluminum chloride solution to the ethanol solvent of 1:1, heating the solution to 90 ℃ by using high-frequency electromagnetic waves with the frequency of 915MHz, stirring and reacting for 75min, carrying out solid-liquid separation to obtain aluminum fluoride precipitate and filtrate I, and carrying out air floatation treatment on the filtrate I to obtain an organic solvent I (diethyl carbonate and fluoroethylene carbonate) and filtrate II.
(4) And adding a certain amount of lime into the filtrate II, regulating the pH value of the solution to 7.1, stirring and reacting for 10min, and then carrying out solid-liquid separation to obtain solid precipitated calcium borate and filtrate III.
(5) Rectifying the filtrate III, and separating out an ethanol solvent to obtain a mixed solution I; the ethanol solvent is reused for the treatment of the LiBF4 condensed electrolyte.
(6) And (3) separating the organic matters in the mixed solution I by using an adsorption resin to obtain a mixed solution II, and removing the resin to obtain an organic solvent II (ethylene carbonate, propylene carbonate and propane sultone).
(7) Separating boron element in the mixed solution II by using boron adsorption resin to obtain a mixed solution III; and (3) after the boron adsorption resin is saturated, desorbing by using a 1mol/L sodium hydroxide solution to obtain a sodium borate solution.
(8) Carrying out nanofiltration treatment on the mixed solution III to obtain lithium chloride filtrate and calcium chloride concentrate; evaporating and drying the lithium chloride solution and the calcium chloride solution respectively to obtain solid lithium chloride and solid calcium chloride.
Example 2
LiBF 4 The components of the condensed electrolyte are as follows: taking a mixture of cellulose acetate butyrate (70000) and vinylidene fluoride and hexafluoropropylene copolymer (80000) =2:8 as a polymer; ethylene carbonate, propylene carbonate and diethyl carbonate are used as organic solvents; fluoroethylene carbonate and propane sultone are used as additives; liBF 4 And (3) preparing lithium salt.
(1) Discharging and disassembling the waste condensed lithium ion battery, and taking out LiBF 4 An electrolyte in a condensed state.
(2) The LiBF is prepared by 4 Soaking the condensed electrolyte in an ethanol solvent with the volume of 2.5 times, continuously stirring for 8 hours at 70 ℃ and 1.4Bar, and then carrying out solid-liquid separation on the electrolyte by a filter press to obtain a solid polymer (cellulose acetate butyrate, copolymer of vinylidene fluoride and hexafluoropropylene) and ethanol leaching solution; the solid polymer can be reused for the production of the condensed electrolyte after being washed by ethanol for the second time.
(3) Adding an aluminum chloride solution into the ethanol leaching solution according to the mole ratio of Al to F of 1:3 and the volume ratio of the aluminum chloride solution to the ethanol solvent of 1:1, heating the solution to 90 ℃ by using high-frequency electromagnetic waves with the frequency of 915MHz, stirring and reacting for 70min, carrying out solid-liquid separation to obtain aluminum fluoride precipitate and filtrate I, and carrying out air floatation treatment on the filtrate I to obtain an organic solvent I (diethyl carbonate and fluoroethylene carbonate) and filtrate II.
(4) And adding a certain amount of lime into the filtrate II, regulating the pH value of the solution to 7.0, stirring and reacting for 10min, and then carrying out solid-liquid separation to obtain solid precipitated calcium borate and filtrate III.
(5) Rectifying the filtrate III, and separating out an ethanol solvent to obtain a mixed solution I; the ethanol solvent is reused for LiBF 4 And (5) treating the condensed electrolyte.
(6) And (3) separating the organic matters in the mixed solution I by using an adsorption resin to obtain a mixed solution II, and removing the resin to obtain an organic solvent II (ethylene carbonate, propylene carbonate and propane sultone).
(7) Separating boron element in the mixed solution II by using boron adsorption resin to obtain a mixed solution III; and (3) after the boron adsorption resin is saturated, desorbing by using a 1mol/L sodium hydroxide solution to obtain a sodium borate solution.
(8) Carrying out nanofiltration treatment on the mixed solution III to obtain lithium chloride filtrate and calcium chloride concentrate; evaporating and drying the lithium chloride solution and the calcium chloride solution respectively to obtain solid lithium chloride and solid calcium chloride.
Example 3
LiBF 4 The components of the condensed electrolyte are that a mixture of cellulose acetate butyrate (70000) and cellulose propionate butyrate (75000) and vinylidene fluoride and hexafluoropropylene copolymer (80000) =3:3:4 is used as a polymer; ethylene carbonate, propylene carbonate and diethyl carbonate are used as organic solvents; fluoroethylene carbonate and propane sultone are used as additives; liBF 4 And (3) preparing lithium salt.
(1) Discharging and disassembling the waste condensed lithium ion battery, and taking out LiBF 4 An electrolyte in a condensed state.
(2) The LiBF is prepared by 4 Soaking the condensed electrolyte in 3 times volume of ethanol solvent at 75Continuously stirring for 10 hours at the temperature of 1.2Bar, and then carrying out solid-liquid separation on the mixture by a filter press to obtain a solid polymer (cellulose acetate butyrate, cellulose propionate butyrate, copolymer of vinylidene fluoride and hexafluoropropylene) and ethanol leaching solution; the solid polymer can be reused for the production of the condensed electrolyte after being washed by ethanol for the second time.
(3) Adding an aluminum chloride solution into the ethanol leaching solution according to the mole ratio of Al to F of 1:3 and the volume ratio of the aluminum chloride solution to the ethanol solvent of 1:1, heating the solution to 90 ℃ by using high-frequency electromagnetic waves with the frequency of 915MHz, stirring and reacting for 80min, carrying out solid-liquid separation to obtain aluminum fluoride precipitate and filtrate I, and carrying out air floatation treatment on the filtrate I to obtain an organic solvent I (diethyl carbonate and fluoroethylene carbonate) and filtrate II.
(4) And adding a certain amount of lime into the filtrate II, regulating the pH value of the solution to 7.2, stirring and reacting for 10min, and then carrying out solid-liquid separation to obtain solid precipitated calcium borate and filtrate III.
(5) Rectifying the filtrate III, and separating out an ethanol solvent to obtain a mixed solution I; the ethanol solvent is reused for LiBF 4 And (5) treating the condensed electrolyte.
(6) And (3) separating the organic matters in the mixed solution I by using an adsorption resin to obtain a mixed solution II, and removing the resin to obtain an organic solvent II (ethylene carbonate, propylene carbonate and propane sultone).
(7) Separating boron element in the mixed solution II by using boron adsorption resin to obtain a mixed solution III; and (3) after the boron adsorption resin is saturated, desorbing by using a 1mol/L sodium hydroxide solution to obtain a sodium borate solution.
(8) Carrying out nanofiltration treatment on the mixed solution III to obtain lithium chloride filtrate and calcium chloride concentrate; evaporating and drying the lithium chloride solution and the calcium chloride solution respectively to obtain solid lithium chloride and solid calcium chloride.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art to make and use the present application. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the above-described embodiments, and those skilled in the art, based on the explanation of the present application, should make improvements and modifications without departing from the scope of the present application.
Claims (9)
1. The application provides a method for processing LiBF by high-frequency electromagnetic waves 4 A method for condensing electrolyte and by-producing lithium chloride and calcium borate is characterized in that:
(1) Discharging and disassembling the waste condensed lithium ion battery, and taking out LiBF 4 An electrolyte in a condensed state.
(2) The LiBF is prepared by 4 Soaking the condensed electrolyte in an ethanol solvent with the volume of 2.5-3 times, continuously stirring for 8-10 hours at the temperature of 70-75 ℃ under the pressure of 1.2-1.4 Bar, and then separating the organic solvent, the additive and the lithium salt which are solidified and bound in the polymer from the polymer into the ethanol solvent, and carrying out solid-liquid separation on the solid solvent by a filter press to obtain a solid polymer (carboxylic cellulose and fluorine-containing olefin polymer) and ethanol leaching solution; the solid polymer can be reused for the production of the condensed electrolyte after being washed by ethanol for the second time.
(3) Adding an aluminum chloride solution into the ethanol leaching solution according to the volume ratio of the aluminum chloride solution to the ethanol solvent of 1:1, heating the solution to 90 ℃ by using high-frequency electromagnetic waves with the frequency of 915MHz, stirring and reacting for 70-80 min, thoroughly converting fluorine element in the solution into aluminum fluoride under the catalysis of the electromagnetic waves, carrying out solid-liquid separation to obtain aluminum fluoride precipitate and filtrate I, and carrying out air floatation treatment on the filtrate I to obtain an organic solvent I and filtrate II.
(4) And adding a certain amount of lime into the filtrate II, regulating the pH value of the solution to 7.0-7.2, stirring and reacting for 10min, and then carrying out solid-liquid separation to obtain solid precipitated calcium borate and filtrate III.
(5) Rectifying the filtrate III, and separating out an ethanol solvent to obtain a mixed solution I; the ethanol solvent is reused for LiBF 4 And (5) treating the condensed electrolyte.
(6) And (3) separating the organic matters in the mixed solution I by using an adsorption resin to obtain a mixed solution II, and removing the resin to obtain an organic solvent II.
(7) Separating boron element in the mixed solution II by using boron adsorption resin to obtain a mixed solution III; and (3) after the boron adsorption resin is saturated, desorbing by using a 1mol/L sodium hydroxide solution to obtain a sodium borate solution.
(8) Carrying out nanofiltration treatment on the mixed solution III to obtain lithium chloride filtrate and calcium chloride concentrate; evaporating and drying the lithium chloride solution and the calcium chloride solution respectively to obtain solid lithium chloride and solid calcium chloride.
2. A high frequency electromagnetic wave processing LiBF according to claim 1 4 A method for condensing electrolyte and by-producing lithium chloride and calcium borate is characterized in that: the carboxylic acid cellulose is one or a combination of more of cellulose acetate propionate, cellulose acetate butyrate and cellulose propionate butyrate.
3. A high frequency electromagnetic wave processing LiBF according to claim 1 4 A method for condensing electrolyte and by-producing lithium chloride and calcium borate is characterized in that: the fluorine-containing olefin polymer is one or the combination of more of polyvinylidene fluoride, polyvinylidene fluoride propylene, and copolymer of vinylidene fluoride and hexafluoropropylene.
4. A high frequency electromagnetic wave processing LiBF according to claim 1 4 A method for condensing electrolyte and by-producing lithium chloride and calcium borate is characterized in that: adding aluminum chloride according to the mole ratio of Al to F of 1 to 3, which has the function of converting fluorine element into stable aluminum fluoride precipitate and preventing LiBF 4 Hydrolysis produces highly toxic hydrogen fluoride, and aluminum fluoride can be sold as a product for aluminum production.
5. A high frequency electromagnetic wave processing LiBF according to claim 1 4 A method for condensing electrolyte and by-producing lithium chloride and calcium borate is characterized in that: 3LiBF 4 +4AlCl 3 +9H 2 O＝9HCl+3LiCl+3H 3 BO 3 +4AlF 3 And ∈s a reaction equation for generating aluminum fluoride.
6. A high frequency electromagnetic wave processing LiBF according to claim 1 4 A method for condensing electrolyte and by-producing lithium chloride and calcium borate is characterized in that: the organic solvent I is one or the combination of a plurality of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and fluoroethylene carbonate.
7. A high frequency electromagnetic wave processing LiBF according to claim 1 4 A method for condensing electrolyte and by-producing lithium chloride and calcium borate is characterized in that: the organic solvent II is one or the combination of more of ethylene carbonate, propylene carbonate and propane sultone.
8. A high frequency electromagnetic wave processing LiBF according to claim 1 4 A method for condensing electrolyte and by-producing lithium chloride and calcium borate is characterized in that: the organic solvent I and the organic solvent II can be reused for the production of the condensed electrolyte.
9. A high frequency electromagnetic wave processing LiBF according to claim 1 4 A method for condensing electrolyte and by-producing lithium chloride and calcium borate is characterized in that: the boron element in the electrolyte is recovered in the form of calcium borate, and the calcium borate can be used as a product in the ceramic industry.
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| CN202310703715.2A CN116835613A (en) | 2023-06-03 | 2023-06-03 | LiBF (LiBF) treated by high-frequency electromagnetic waves 4 Method for preparing condensed electrolyte and by-producing lithium chloride and calcium borate |
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| CN202310703715.2A CN116835613A (en) | 2023-06-03 | 2023-06-03 | LiBF (LiBF) treated by high-frequency electromagnetic waves 4 Method for preparing condensed electrolyte and by-producing lithium chloride and calcium borate |
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