CN114759286A - Method for recovering waste electrolyte of lithium ion battery - Google Patents
Method for recovering waste electrolyte of lithium ion battery Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 81
- 239000002699 waste material Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 238000000605 extraction Methods 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 16
- 238000004064 recycling Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 239000002274 desiccant Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 150000004673 fluoride salts Chemical class 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 13
- 159000000002 lithium salts Chemical class 0.000 description 13
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- WVCAATDGXHFREC-UHFFFAOYSA-M potassium;ethyl carbonate Chemical compound [K+].CCOC([O-])=O WVCAATDGXHFREC-UHFFFAOYSA-M 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 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 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application provides a method for recovering waste electrolyte of a lithium ion battery, wherein the waste electrolyte contains lithium hexafluorophosphate, and the method comprises the following steps: s1: adding a saline solution into the collected waste electrolyte to be used as an extracting agent for extraction, separating a lower-layer organic solution from an upper-layer aqueous solution, and recovering the lower-layer organic solution to obtain an organic solvent; s2: adding water-soluble carbonate and/or water-soluble phosphate to the upper aqueous solution in step S1, filtering, and separating to obtain lithium precipitate. The recovery method can realize the efficient separation and recovery of organic solvents and lithium elements in the waste electrolyte, is simple and easy to operate, is economic and environment-friendly, has strong applicability, and can be used for large-scale preparation and production.
Description
Technical Field
The application relates to the technical field of waste resource recovery, in particular to a method for recovering waste electrolyte of a lithium ion battery.
Background
With the rapid development and large-scale application of lithium ion batteries, the number of waste lithium ion batteries is also multiplied, so that the recycling and harmless treatment of resources become the most important factor at present. If the waste can not be effectively recovered in time, the waste of resources and the environmental pollution can be caused. However, large-scale recycling technology at home and abroad is in the beginning stage, and research on the technology mainly focuses on metal elements which are easy to operate and have high economic value, such as nickel, cobalt, aluminum, copper and the like, and has little research on other components of the battery. Especially for the electrolyte, the components are complex, the hydrolysis is easy, the environmental pollution is serious, the recovery difficulty is high, and the cost is high. In order to meet the requirement of environmental protection, only some simple treatments are usually carried out in the recovery process, and resource recovery is not realized.
Currently, the most studied electrolyte recovery processes are as follows: supercritical extraction, vacuum rectification, alkali liquor absorption and mechanical method. Supercritical extraction method generally adopts supercritical state CO2The method does not damage the molecular structure of the electrolyte, is environment-friendly, has complex process, harsh conditions and higher cost, and is not suitable for large-scale recovery of the waste electrolyte. The product obtained by the vacuum distillation method has high purity and relatively high recovery rate, but the process is complex, the energy consumption is high, and the recovery profit is low. Compared with other methods, the alkali liquor absorption method has simpler process, but can generate more waste water, waste gas and the like in the recovery process to cause secondary pollution to the environment. The mechanical method is generally complex to operate and low in recovery rate, and is not suitable for industrial large-scale production. Therefore, the research and development of a simple and effective electrolyte recovery method with low cost has important research significance and application value.
Disclosure of Invention
In order to solve the problems, the application provides a method for recovering waste electrolyte of a lithium ion battery.
An embodiment of the present application provides a method for recovering a waste electrolyte of a lithium ion battery, where the waste electrolyte contains lithium hexafluorophosphate, including the following steps:
s1: adding a saline solution into the collected waste electrolyte to be used as an extracting agent for extraction, separating a lower-layer organic solution and an upper-layer aqueous solution, and recovering the lower-layer organic solution to obtain an organic solvent;
s2: adding water-soluble carbonate and/or water-soluble phosphate to the upper aqueous solution in step S1, filtering, and separating to obtain lithium precipitate.
In some embodiments, the volume ratio of the saline solution to the waste electrolyte is 1-10.
In some embodiments, the salt in the aqueous salt-containing solution is at least one of sodium chloride, potassium chloride, sodium phosphate, sodium sulfate, or potassium sulfate.
In some embodiments, the concentration of the saline solution is between 10% and 100%.
In some embodiments, the water-soluble carbonate is sodium carbonate and the water-soluble phosphate is sodium phosphate.
In some embodiments, step S1 is followed by: and adding the upper-layer aqueous solution serving as an extracting agent into new waste electrolyte for circular extraction.
Further, heating the upper layer aqueous solution obtained after the cyclic extraction for many times, adding quicklime water or calcium hydroxide aqueous solution after full reaction, filtering, and separating to obtain the precipitate of phosphate and fluoride salt.
Further, the heating temperature is 100-150 ℃.
In some embodiments, the recovering the lower layer organic solution to obtain the organic solvent in step S1 includes:
and adding a drying agent into the upper layer organic liquid for dewatering, standing for a period of time, and then rectifying and purifying to obtain the organic solvent.
In some embodiments, the extraction rate of lithium element in the waste electrolyte is greater than 90%.
Compared with the prior art, the beneficial effect of this application is:
according to the recovery method, the salt-containing aqueous solution is added into the waste electrolyte, so that the solution and the solute in the electrolyte can be efficiently separated, the organic solvent obtained after separation can be purified and recycled, and the lithium element in the upper-layer aqueous solution can be efficiently extracted. The method is simple and feasible, economical, environment-friendly and high in applicability, and can be used for large-scale preparation and production.
Drawings
Fig. 1 is a flowchart of a method for recovering waste electrolyte of a lithium ion battery according to an embodiment of the present disclosure.
FIG. 2 is an optical diagram of the salt-containing aqueous solution described in examples 1-3 when extracted 5 times repeatedly.
Detailed Description
The present application is further illustrated below with reference to examples. These examples are intended to be illustrative of the present application only and are not intended to limit the scope of the present application. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present disclosure are intended to be covered by the claims.
One embodiment of the present application provides a method for recovering a waste electrolyte of a lithium ion battery, where the waste electrolyte contains lithium hexafluorophosphate, including the following steps:
s1: adding a saline solution into the collected waste electrolyte to be used as an extracting agent for extraction, separating a lower-layer organic solution from an upper-layer aqueous solution, and recovering the lower-layer organic solution to obtain an organic solvent;
s2: adding water-soluble carbonate and/or water-soluble phosphate to the upper aqueous solution in step S1, filtering, and separating to obtain lithium precipitate.
The lithium ion battery described in the present application may be any chemical type of battery, such as a waste lithium iron phosphate battery, a waste ternary material battery (containing lithium, nickel, cobalt, manganese or aluminum), and the like, and the waste electrolyte includes electrolyte remaining in the waste lithium ion battery and spent electrolyte generated in an enterprise production process. The waste electrolyte mainly comprises an organic solvent and electrolyte lithium salt, wherein the organic solvent is generally carbonates, such as dimethyl carbonate, potassium carbonate ethyl ester or ethylene carbonateThe electrolyte lithium salt is typically lithium hexafluorophosphate (LiPF)6)。
This application utilizes in the electrolyte organic solvent and electrolyte lithium salt in the difference of aquatic solubility, carries out high-efficient separation recovery to its component through adding salt solution to old and useless electrolyte, and the upper organic solution that obtains after the separation can be in the air stable storage, and lithium element in the electrolyte then can selectively extract in the salt solution that contains. Lithium can be efficiently extracted from a large amount of electrolyte by a precipitation method. The method is simple to operate, economic and environment-friendly, can realize the maximum recycling of resources in the waste electrolyte, and is suitable for large-scale production and treatment of enterprises.
In the embodiment, the volume ratio of the saline solution to the waste electrolyte is 1-10.
In this embodiment, the salt in the aqueous salt-containing solution is at least one of sodium chloride, potassium chloride, sodium sulfate, or potassium sulfate.
In the present embodiment, the concentration of the saline solution is 10% to 100%.
Research shows that when pure water is added into the waste electrolyte, the volume ratio of the pure water to the waste electrolyte is 1: 1, the waste electrolyte is completely miscible with pure water. When the volume ratio is higher than 1: in the 1 hour, only a small amount of waste electrolyte is separated out. When a certain amount of salt substances are added into pure water, the saline solution is added into the waste electrolyte, the waste electrolyte and the saline solution are completely layered, and most of the most valuable lithium in the waste electrolyte is concentrated into the saline solution. This is probably because the addition of salt-like substances to the aqueous solution effectively increases the ionic strength in the aqueous phase, increases the polarity, and promotes the separation of the aqueous phase from the organic phase. At the same time, the electrolyte lithium salt displaces lithium into the saline solution due to the action with the salt solution.
It is understood that when the concentration of the saline solution is high (high saturation), the lithium precipitate obtained by separation and recovery may contain a part of the salt substances precipitated from the saturated saline solution, and then the pure lithium precipitate may be obtained by precipitation and separation through simple dissolution by adding water.
In this embodiment, the water-soluble carbonate is sodium carbonate, and the water-soluble phosphate is sodium phosphate.
In the present embodiment, step S1 is followed by: and adding the upper-layer aqueous solution serving as an extracting agent into new waste electrolyte for circular extraction.
Further, heating the upper layer aqueous solution obtained after the cyclic extraction for many times, adding quicklime water or calcium hydroxide aqueous solution after full reaction, filtering, and separating to obtain the precipitate of phosphate and fluoride salt.
Further, the heating temperature is 100-150 ℃.
In the application, the upper-layer aqueous solution can be recycled as an extracting agent, and the waste electrolyte is extracted for multiple times. When the concentration of fluorine and phosphorus elements in the solution reaches a certain degree, the upper layer aqueous solution is heated to more than 100 ℃, and the fluorine and phosphorus elements in the waste electrolyte can be completely hydrolyzed into HF and H3PO4Therefore, fluorine and phosphorus elements can be separated and recovered by a precipitation method, so that all the lithium, fluorine and phosphorus elements in the waste electrolyte can be efficiently separated and recovered.
In this embodiment, the step S1 of "recovering the lower organic solution to obtain the organic solvent" includes:
and adding a drying agent into the lower-layer organic solution for dewatering, standing for a period of time, and then rectifying and purifying to obtain the organic solvent.
Wherein, the drying agent can be anhydrous sodium sulfate and a dry molecular sieve; the standing time can be 12 h.
In this embodiment, the extraction rate of lithium element in the waste electrolyte is greater than 90%.
In this application, the accessible contains salt aqueous solution and carries out a lot of extraction to same batch of old and useless electrolyte, and when extracting for the first time, contains salt aqueous solution and can absorb a small amount of electrolyte solution to organic solution's separation rate is about 90%, and contains a certain amount of lithium salt in the organic solution of separation. After multiple times of extraction, the concentration of lithium in the separated lower-layer organic solution is lower than 5ppm, and the extraction rate of the lithium in the whole waste electrolyte can reach 99.93%.
The following detailed description will be made of the method for recovering waste electrolyte of lithium ion battery according to the present application by using specific examples.
It is to be understood that the concentrations and the amounts of the sodium carbonate solution and the calcium hydroxide solution in the examples of the present application are not particularly limited, and the amounts may be changed according to specific experiments.
Example 1
The embodiment provides a method for recovering waste electrolyte of a lithium ion battery, a flow chart of which is shown in fig. 1, and the method specifically comprises the following steps:
s1: in the collected waste electrolyte, the volume ratio of 1: 1, adding 100 percent saturated sodium chloride deionized water solution (namely the volume ratio is 1: 1), stirring and mixing uniformly, then standing for layering, and separating out lower-layer organic solution and upper-layer aqueous solution.
S2: to the lower organic solution obtained in step S1, the ratio of 1: adding a new 100% saturated sodium chloride deionized water solution according to the volume ratio of 1, repeating for 3 times, respectively adding anhydrous sodium sulfate and a dry molecular sieve into the finally obtained lower-layer organic solution, standing for half a day, and then rectifying and purifying to obtain pure dimethyl carbonate, potassium carbonate ethyl ester and ethylene carbonate.
S3: the upper aqueous solution obtained in step S1 was mixed in the following ratio of 1: 1, adding the solution into new waste electrolyte again, repeatedly extracting and separating for 5 times, adding a certain amount of sodium carbonate solution into the finally obtained upper-layer aqueous solution, filtering, and separating to obtain lithium carbonate precipitate and filtrate; then adding a certain amount of calcium hydroxide solution into the filtrate, heating to 140 ℃, fully reacting, filtering, and separating to obtain a mixture precipitate of calcium phosphate and calcium fluoride.
Example 2
The embodiment provides a method for recovering waste electrolyte of a lithium ion battery, wherein the concentration of a saturated sodium chloride deionized water solution is 60%, and the rest steps are the same as those in embodiment 1.
Example 3
The embodiment provides a method for recovering waste electrolyte of a lithium ion battery, wherein the concentration of the saturated sodium chloride deionized water solution is 30%, and the rest steps are the same as those in the embodiment 1.
Analysis of results
The lithium salt concentration in the waste electrolyte in example 1 was monitored by using an inductively coupled plasma emission spectrometer, the initial lithium salt concentration in the waste electrolyte was 7000ppm, as shown in table 1, and the waste electrolyte was extracted cyclically 3 times, after the first extraction, the lithium salt concentration in the lower organic solution obtained by separation was reduced to 510ppm, and after the 3 rd extraction separation, the lithium salt concentration was reduced to 5 ppm. It can be known that after multiple extractions, the concentration of lithium ions in the separated organic solution is lower than 5ppm, and the extraction rate of lithium ions in the whole waste electrolyte can reach 99.93%.
TABLE 1 lithium salt concentration at 3 extractions of the same spent electrolyte in example 1
| Number of extractions | Lithium salt concentration (ppm) |
| 1 | 510 |
| 2 | 78 |
| 3 | 5 |
In examples 1 to 3, saline solutions with different concentrations are respectively adopted to extract the waste electrolyte. Fig. 2 is an optical picture of the same saline solution after 5 extractions of different spent electrolytes. As can be seen from FIG. 2, the same saline solution can be obviously layered with the lower organic solution in the waste electrolyte after being reused for 5 times, so that the high-efficiency recovery of the waste electrolyte is realized. As can be further seen from table 2, the lithium element concentration in the saline solution is increased by multiple times after each extraction, and the lithium salt can be efficiently extracted after the same saline solution on the surface is reused for 5 times.
Table 2 lithium salt concentration after 5 repeated extractions of the saline solution as described in examples 1-3
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present application and not for limiting, and although the present application is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application.
Claims (10)
1. A method for recovering waste electrolyte of a lithium ion battery, wherein the waste electrolyte contains lithium hexafluorophosphate, is characterized by comprising the following steps:
s1: adding a saline solution into the collected waste electrolyte to be used as an extracting agent for extraction, separating a lower-layer organic solution from an upper-layer aqueous solution, and recovering the lower-layer organic solution to obtain an organic solvent;
s2: adding water-soluble carbonate and/or water-soluble phosphate to the upper aqueous solution in step S1, filtering, and separating to obtain lithium precipitate.
2. The method for recycling the waste electrolyte of the lithium ion battery according to claim 1, wherein the volume ratio of the saline solution to the waste electrolyte is 1-10.
3. The method for recycling the waste electrolyte of the lithium ion battery according to claim 1, wherein the salt in the saline solution is at least one of sodium chloride, potassium chloride, sodium phosphate, sodium sulfate or potassium sulfate.
4. The method for recycling spent electrolyte of lithium ion batteries according to claim 1, wherein the concentration of said salt-containing aqueous solution is 10% to 100%.
5. The method for recycling spent electrolyte of lithium ion batteries according to claim 1, wherein said water-soluble carbonate is sodium carbonate and said water-soluble phosphate is sodium phosphate.
6. The method for recycling waste electrolyte of lithium ion battery according to claim 1, wherein step S1 is followed by the steps of: and adding the upper-layer aqueous solution serving as an extracting agent into new waste electrolyte for circular extraction.
7. The method for recycling waste electrolyte of lithium ion battery as claimed in claim 6, wherein the upper aqueous solution obtained after the cyclic extraction is performed for a plurality of times is heated, after the sufficient reaction, quicklime water or calcium hydroxide aqueous solution is added, and the precipitate of phosphate and fluoride salt is obtained by filtration and separation.
8. The method for recycling the waste electrolyte of the lithium ion battery according to claim 7, wherein the heating temperature is 100-150 ℃.
9. The method for recycling spent electrolyte of lithium ion batteries according to claim 1, wherein the step of recycling the lower organic solution to obtain the organic solvent in step S1 comprises:
and adding a drying agent into the lower-layer organic solution for dewatering, standing for a period of time, and then rectifying and purifying to obtain the organic solvent.
10. The method for recycling spent electrolyte of lithium ion batteries according to claim 1, wherein the extraction rate of lithium element in the spent electrolyte is greater than 90%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210601906.3A CN114759286A (en) | 2022-05-30 | 2022-05-30 | Method for recovering waste electrolyte of lithium ion battery |
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| WO2024055518A1 (en) * | 2022-09-16 | 2024-03-21 | 广东邦普循环科技有限公司 | Method for recycling lithium from electrolyte of lithium ion battery |
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