A device and method for full recovery of waste lithium battery electrolyte

Abstract

The application relates to the technical field of electrolyte recovery, and provides a device and a method for full recovery of waste lithium battery electrolyte, the device for full recovery of the waste lithium battery electrolyte comprising a solvent extractor, a first condenser, a conveying piece, an absorption tank, a first valve, a first solvent storage tank and a second valve, the first condenser being communicatively arranged in the solvent extractor, the conveying piece having a flow guide section, a first shunt section and a second shunt section which are communicated, the first shunt section and the second shunt section being arranged in parallel, the absorption tank being communicatively arranged in the first shunt section, the first valve being communicatively arranged in the first shunt section, one end of the first solvent storage tank being communicatively arranged with the second shunt section, the other end of the first solvent storage tank being communicatively arranged with the solvent extractor, and the second valve being communicatively arranged in the second shunt section. The application can solve the problem that the solvent and the electrolyte in the electrolyte cannot be recovered, and the resources of the solvent and the electrolyte are wasted.

Description

Technical Field

[0001] This application relates to the field of electrolyte recycling technology, and in particular to an apparatus and method for the complete recycling of waste lithium battery electrolyte. Background Technology

[0002] A battery consists of a positive electrode, a negative electrode, and an electrolyte. The electrolyte, as the core component of the battery, contains a large amount of flammable organic solvents, the electrolyte lithium hexafluorophosphate, and its decomposition products.

[0003] When recycling batteries, the batteries can be crushed and pyrolyzed first, then the volatile gases can be condensed to obtain the electrolyte solvent, which is then sprayed with alkaline solution, and finally the sprayed liquid is disposed of as hazardous waste.

[0004] In related technologies, it is impossible to recover the solvent and electrolyte in the electrolyte, which will result in the waste of solvent and electrolyte resources. Summary of the Invention

[0005] This application provides an apparatus and method for the complete recycling of waste lithium battery electrolyte, which can solve the problem of the inability to recycle solvents and electrolytes in electrolytes, resulting in the waste of solvent and electrolyte resources.

[0006] To achieve the above objectives, this application adopts the following technical solution:

[0007] In a first aspect, this application provides an apparatus for the complete recycling of waste lithium battery electrolyte, comprising:

[0008] Solvent extractor, used to contain the filtrate from lithium batteries;

[0009] The first condenser is connected to the solvent extractor;

[0010] The conveying component has a connected guide section, a first diversion section and a second diversion section, which are arranged in parallel.

[0011] An absorption tank is connected and installed in the first diversion section;

[0012] The first valve is connected to the first diversion section and is used to open or close the connection between the first diversion section and the absorption tank.

[0013] A first solvent storage tank, one end of which is connected to a second diversion section, and the other end of which is connected to a solvent extractor;

[0014] The second valve is connected to the second diversion section and is used to open or close the connection between the second diversion section and the first solvent storage tank.

[0015] In some embodiments, the conveyor has a third diversion section communicating with the guide section, the third diversion section being arranged in parallel with the first diversion section;

[0016] The equipment for the complete recycling of waste lithium battery electrolyte also includes:

[0017] The second solvent storage tank is connected to the third diversion section;

[0018] The third valve is connected to the third diversion section. The third valve is used to open or close the connection between the third diversion section and the second solvent storage tank.

[0019] Vacuum components are connected to the solvent extractor.

[0020] In some embodiments, the absorption tank has a first output terminal and a second output terminal;

[0021] The equipment for the complete recycling of waste lithium battery electrolyte also includes:

[0022] The second condenser has one end connected to the first output end and the other end connected to the solvent extractor.

[0023] The hydrolysis reactor is connected to the absorption tank through the second output end, and the hydrolysis reactor is also connected to the solvent extractor.

[0024] In some implementations, it also includes:

[0025] An electrolyte leaching device is connected to a solvent extractor and is used to transport the filtrate to the solvent extractor; the electrolyte leaching device is also connected to a first solvent storage tank.

[0026] In some implementations, it also includes:

[0027] The first filter element is connected to the hydrolysis reactor; the interior of the first filter element is divided into an upper filtrate layer and a lower sediment layer.

[0028] An organic phase separator has an inlet end, a first outlet end and a second outlet end. The inlet end is connected to the upper filtrate layer and the first outlet end is connected to the electrolyte leaching device.

[0029] The primary fluoride extractor is connected to the lower precipitate layer.

[0030] In some implementations, it also includes:

[0031] A phosphorus extractor is connected to the second liquid outlet end;

[0032] The second filter element is connected to the hydrolysis reactor;

[0033] An impurity metal separator is connected to the second filter element;

[0034] The third filter element is connected to the impurity metal separator and is also connected to the primary fluorine extractor.

[0035] The fourth filter element is connected to the primary fluoride extractor;

[0036] A lithium extractor is connected to the fourth filter element;

[0037] The fifth filter element is connected to the lithium extractor;

[0038] A secondary fluoride extractor is connected to the fifth filter element;

[0039] The sixth filter element is connected to the secondary fluoride extractor.

[0040] Secondly, this application provides a method for the complete recycling of waste lithium battery electrolyte, applied to an apparatus for the complete recycling of waste lithium battery electrolyte, the method comprising the following steps:

[0041] The filtrate from the lithium battery is delivered to the solvent extractor;

[0042] Open the first valve, close the second valve, and adjust the first condenser to the first temperature so that the first part of the filtrate passes through the first condenser, the guide section of the conveying component, and the first diversion section of the conveying component in sequence, and is conveyed to the absorption tank.

[0043] Close the first valve, open the second valve, and adjust the first condenser to the second temperature so that the second volume of filtrate passes sequentially through the first condenser, the guide section, and the second diversion section of the conveying component, and is then transported to the first solvent storage tank.

[0044] In some embodiments, when opening the first valve and closing the second valve, the method further includes:

[0045] The third valve of the device for the complete recycling of waste lithium battery electrolyte is closed.

[0046] In some embodiments, when closing the first valve and opening the second valve, the method further includes:

[0047] The third valve of the device for the complete recycling of waste lithium battery electrolyte is closed.

[0048] In some implementations, the following steps are also included:

[0049] Close the first valve, close the second valve, and open the third valve; adjust the first condenser to the third temperature so that the third volume of filtrate passes sequentially through the first condenser, the guide section, and the third diversion section of the conveying component, and is then transported to the second solvent storage tank.

[0050] In some implementations, the following steps are also included:

[0051] The first portion of the filtrate in the absorption tank is sequentially transported to the hydrolysis reactor and the first filter element.

[0052] The filtrate in the upper filtrate layer of the first filter element is transported to the organic phase separator, and the solids in the lower sedimentation layer of the first filter element are transported to the primary fluoride extractor.

[0053] The aqueous phase of the filtrate in the organic phase separator is transported to the phosphorus extractor, and the organic phase of the filtrate in the organic phase separator is transported to the electrolyte leaching unit;

[0054] The liquid in the phosphate extractor is sequentially passed through the second filter element, the impurity metal separator, the third filter element, the primary fluorine extractor, the fourth filter element, the lithium extractor, the fifth filter element, and the secondary fluorine extractor before being conveyed to the sixth filter element.

[0055] In some embodiments, nitrogen gas is introduced into the hydrolysis reactor, and water, 1%-2% hydrochloric acid and tributyl phosphate are added. The volume of water is 20%-30% of the volume of the liquid in the reactor, and the volume of hydrochloric acid is 2%-8% of the volume of the liquid in the reactor. The mass ratio of tributyl phosphate to lithium hexafluorophosphate in the waste electrolyte is 0.005-0.01:1. The internal pressure of the hydrolysis reactor is 0.2MPa-0.5MPa, the hydrolysis temperature is 30℃-50℃, and the hydrolysis time is 30min-90min.

[0056] And / or, ferric chloride is added to the phosphorus extractor, with the ratio of ferric chloride to lithium hexafluorophosphate in the waste electrolyte being 1.1~1.3:1;

[0057] And / or, the pH of the impurity metal separator is adjusted to 3-4 with a 5% sodium hydroxide solution and a 5% sodium carbonate solution is added.

[0058] And / or, add 5%~10% calcium hydroxide suspension to the primary fluoride extractor, with the ratio of calcium hydroxide to lithium hexafluorophosphate in the waste electrolyte being 2.8~2.9:1, and adjust the pH to 9~10 with 5% sodium hydroxide solution, raise the temperature to 50℃~70℃, and stir for 60min~90min;

[0059] And / or, carbon dioxide is introduced into the lithium extractor to maintain a pressure of 0.2 MPa to 0.3 MPa inside the lithium extractor, and the pressure is maintained at an internal temperature of 60℃ to 80℃ for 40 min to 120 min;

[0060] And / or, add 5%~10% calcium chloride solution to the secondary fluoride extractor, with the ratio of calcium chloride to lithium hexafluorophosphate in the waste electrolyte being 0.2-0.6:1. Adjust the pH to 9~10 with 5% sodium hydroxide solution and stir the reaction for 30min~60min.

[0061] In some implementations, the following steps are also included:

[0062] The electrolyte leaching solution in the electrolyte extractor is transferred to the solvent extractor;

[0063] The second volume of filtrate in the first solvent storage tank is delivered to the solvent extractor;

[0064] The gas in the absorption tank is then transported to the solvent extractor after passing through the second condenser.

[0065] This waste lithium battery electrolyte recycling device uses a solvent extractor to distill the lithium battery filtrate, separating the solvent, electrolyte, and decomposition products. A first condenser cools the distilled fraction. An absorption tank absorbs the distilled decomposition products, phosphorus pentafluoride and hydrogen fluoride. A first solvent storage tank stores the distilled solvent. Electrolytes and residues in the filtrate are stored in the solvent extractor. A first and second valve control the flow of the distilled fraction. When the first valve is open and the second valve is closed, the fraction is transported to the absorption tank; when the first valve is closed and the second valve is open, the fraction is transported to the first solvent storage tank.

[0066] Therefore, the device for the complete recycling of waste lithium battery electrolyte provided in the embodiments of this application can solve the problem of the waste of solvent and electrolyte resources caused by the inability to recycle the solvent and electrolyte in the electrolyte. Attached Figure Description

[0067] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0068] Figure 1 A schematic diagram of the main structure of the device for the complete recycling of waste lithium battery electrolyte provided in the embodiments of this application;

[0069] Figure 2 A flowchart illustrating the method for the complete recycling of waste lithium battery electrolyte provided in this application embodiment.

[0070] Explanation of reference numerals in the attached figures:

[0071] 100-Solvent Extractor;

[0072] 101 - First condenser;

[0073] 102-Conveying component; 1021-Guiding section; 1022-First diversion section; 1023-Second diversion section; 1024-Third diversion section;

[0074] 103 - Absorption tank; 1031 - First output terminal; 1032 - Second output terminal;

[0075] 104 - First valve;

[0076] 105 - First solvent storage tank;

[0077] 106 - Second valve;

[0078] 107 - Second solvent storage tank;

[0079] 108 - Third valve;

[0080] 109 - Vacuum components;

[0081] 110 - Second condenser;

[0082] 111-Hydrolysis reactor;

[0083] 112 - Electrolyte leaching device;

[0084] 113 - First filter element;

[0085] 114 - Organic phase separator; 1141 - Inlet; 1142 - First outlet; 1143 - Second outlet;

[0086] 115 - Primary Fluoride Extractor;

[0087] 116-Phosphorus extractor;

[0088] 117 - Second filter element;

[0089] 118 - Impurity Metal Separator;

[0090] 119 - Third filter element;

[0091] 120 - Fourth filter element;

[0092] 121-Lithium Extractor;

[0093] 122 - Fifth filter element;

[0094] 123-Secondary Fluoride Extractor;

[0095] 124 - Sixth filter element. Detailed Implementation

[0096] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0097] In the prior art, lithium battery electrolytes contain organic solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate (EC), diethyl carbonate (DEC), and methyl ethyl carbonate (EMC), as well as the electrolyte lithium hexafluorophosphate (LiPF6) and trace metal elements (cobalt Co, nickel Ni, etc.).

[0098] Dimethyl carbonate begins to decompose significantly at temperatures above 150 degrees Celsius, producing methanol and carbon dioxide. At temperatures above 200 degrees Celsius, the decomposition accelerates, and byproducts such as formaldehyde and methane may also be produced.

[0099] Lithium hexafluorophosphate begins to decompose significantly into phosphorus pentafluoride (PF5) and lithium fluoride (LiF) precipitates above 60 degrees Celsius, and the rate of decomposition reaction increases with increasing temperature.

[0100] Furthermore, both phosphorus pentafluoride and hydrogen fluoride are soluble in dimethyl carbonate.

[0101] Furthermore, phosphorus pentafluoride can react with water to produce phosphoryl fluoride (i.e., POF3) and hydrogen fluoride (i.e., HF). The phosphoryl fluoride will further react with water to produce phosphoric acid (i.e., H3PO4) and hydrogen fluoride gas.

[0102] In addition, lithium hexafluorophosphate will decompose under the catalysis of water, producing phosphoryl fluoride, lithium fluoride (i.e., LiF) precipitate and hydrogen fluoride gas. The phosphoryl fluoride will further react with water to produce phosphoric acid (i.e., H3PO4) and hydrogen fluoride gas.

[0103] Furthermore, hydrogen fluoride is miscible with water in any proportion at room temperature (i.e., 20°C).

[0104] Therefore, when the battery is pyrolyzed after being broken (pyrolysis temperature greater than or equal to 200 degrees Celsius), the organic solvent dimethyl carbonate in the electrolyte and the electrolyte lithium hexafluorophosphate will volatilize. The hydrogen fluoride gas produced by the volatilization of lithium hexafluorophosphate will be miscible with the solvent in the alkaline solution, making it impossible to recover the solvent and electrolyte in the electrolyte, resulting in a waste of solvent and electrolyte resources.

[0105] To overcome the shortcomings of existing technologies, a solvent extractor is installed to distill the filtrate of lithium batteries, separating the solvent, electrolyte, and decomposition products from the electrolyte in the filtrate. A first condenser is installed to cool the distilled fraction. An absorption tank is installed to absorb the distilled decomposition products, phosphorus pentafluoride and hydrogen fluoride. A first solvent storage tank is installed to store the distilled solvent. The electrolyte and residual substances in the filtrate are stored in the solvent extractor. A first valve and a second valve are installed to control the flow of the distilled fraction. When the first valve is open and the second valve is closed, the fraction can be transported to the absorption tank. When the first valve is closed and the second valve is open, the fraction can be transported to the first solvent storage tank.

[0106] Therefore, the device for the complete recycling of waste lithium battery electrolyte provided in the embodiments of this application can solve the problem of the waste of solvent and electrolyte resources caused by the inability to recycle the solvent and electrolyte in the electrolyte.

[0107] The contents of this application will now be described in detail with reference to the accompanying drawings, so that those skilled in the art can have a clearer and more detailed understanding of the contents of this application.

[0108] like Figure 1As shown in the figure, this application provides an apparatus for the complete recycling of waste lithium battery electrolyte, including: a solvent extractor 100, a first condenser 101, a conveying component 102, an absorption tank 103, a first valve 104, a first solvent storage tank 105, and a second valve 106. The solvent extractor 100 is used to contain the filtrate from the lithium battery. The first condenser 101 is connected to the solvent extractor 100. The conveying component 102 has a connecting guide section 1021, a first diversion section 1022, and a second diversion section 1023. The first diversion section 1022 and the second diversion section 1023 are connected in parallel. The receiving tank 103 is connected to the first diversion section 1022, and the first valve 104 is connected to the first diversion section 1022. The first valve 104 is used to open or close the connection between the first diversion section 1022 and the absorption tank 103. One end of the first solvent storage tank 105 is connected to the second diversion section 1023, and the other end of the first solvent storage tank 105 is connected to the solvent extractor 100. The second valve 106 is connected to the second diversion section 1023 and is used to open or close the connection between the second diversion section 1023 and the first solvent storage tank 105.

[0109] The following sections provide a detailed description of the specific structure of the apparatus and method for the complete recycling of waste lithium battery electrolyte, as well as various possible implementation methods.

[0110] It should be noted that the fraction flowing out of the first condenser 101 can enter the absorption tank 103 after passing through the first diversion section 1022 and the first valve 104, so that the decomposition products phosphorus pentafluoride and hydrogen fluoride in the filtrate can enter the absorption tank 103.

[0111] It should be noted that water is provided in the absorption tank 103. The water can react with phosphorus pentafluoride in the filtrate to produce phosphoric acid and hydrogen fluoride, and dissolve the hydrogen fluoride.

[0112] It is understandable that phosphorus pentafluoride and hydrogen fluoride can be absorbed through the above-described embodiments.

[0113] It should be noted that the fraction flowing out of the first condenser 101 can enter the first solvent storage tank 105 after passing through the second diversion section 1023 and the second valve 106, so that the solvent in the filtrate can enter the absorption tank 103.

[0114] It should be noted that when storing the distilled solvent in the first solvent storage tank 105, the internal temperature of the solvent extractor 100 can be adjusted to above 80 degrees Celsius so that dimethyl carbonate, diethyl carbonate, ethylene carbonate, diethyl carbonate, and methyl ethyl carbonate can simultaneously enter the first solvent storage tank 105 as fractions. Alternatively, the internal temperature of the solvent extractor 100 can be adjusted to 50 to 70 degrees Celsius so that dimethyl carbonate enters the first solvent storage tank 105 as a fraction, and then the internal temperature of the solvent extractor 100 can be adjusted to above 80 degrees Celsius so that diethyl carbonate, ethylene carbonate, diethyl carbonate, and methyl ethyl carbonate can simultaneously enter the first solvent storage tank 105 as fractions. Specifically, the solvent extraction method is not limited and can be selected according to actual usage requirements.

[0115] The conveying component 102 provided in the embodiments of this application has a third diversion section 1024 connected to the guide section 1021. The third diversion section 1024 is arranged in parallel with the first diversion section 1022. The device for full recycling of waste lithium battery electrolyte also includes: a second solvent storage tank 107, a third valve 108 and a vacuum component 109. The second solvent storage tank 107 is connected to the third diversion section 1024. The third valve 108 is connected to the third diversion section 1024. The third valve 108 is used to open or close the connection between the third diversion section 1024 and the second solvent storage tank 107. The vacuum component 109 is connected to the solvent extractor 100.

[0116] It is understood that, through the above-described embodiments, the fraction flowing out of the first condenser 101 can enter the second solvent storage tank 107 after passing through the third diversion section 1024 and the third valve 108, thereby separating dimethyl carbonate in the solvent from other components in the solvent.

[0117] In one embodiment, the solvent extractor 100 is heated to between 30 and 50 degrees Celsius, the first condenser 101 is set to a condensation temperature between 5 and 10 degrees Celsius, then the first valve 104 is opened and the second valve 106 and the third valve 108 are closed. The fraction in the solvent extractor 100 can flow into the absorption tank 103 after passing through the first condenser 101, the guide section 1021, and the first diversion section 1022. The water in the absorption tank 103 can absorb phosphorus pentafluoride and hydrogen fluoride.

[0118] It is understood that the above-described implementation method allows for the pre-separation of corrosive gases from the filtrate, preventing them from being carried over with the organic solvent. The insoluble matter is primarily the organic solvent.

[0119] Furthermore, after no more distillate is discharged from the outlet of the first condenser 101, the first valve 104 is closed, the vacuum component 109 is turned on, and the vacuum degree inside the solvent extractor 100 is set between -0.095 MPa and -0.0905 MPa. The condensation temperature of the first condenser 101 is adjusted to between -10 degrees Celsius and 0 degrees Celsius. The solvent extractor 100 is heated in stages to between 100 degrees Celsius and 120 degrees Celsius. The distillate in the solvent extractor 100 can flow into the first solvent storage tank 105 after passing through the first condenser 101, the guide section 1021, and the second diversion section 1023, or the distillate in the solvent extractor 100 can flow into the second solvent storage tank 107 after passing through the first condenser 101, the guide section 1021, and the third diversion section 1024.

[0120] It should be noted that the staged heating to 100 to 120 degrees Celsius can be done as follows: gradually increase the temperature to 50 to 70 degrees Celsius and maintain it for 40 to 60 minutes, then increase the temperature to 80 to 100 degrees Celsius and maintain it for 20 to 30 minutes, and then continue to increase the temperature to 100 to 120 degrees Celsius.

[0121] Furthermore, when the internal temperature of the solvent extractor 100 is between 50 degrees Celsius and 70 degrees Celsius, the first valve 104 is closed, the second valve 106 is opened, and the third valve 108 is closed. The outflowing fraction flows through the first condenser 101, the guide section 1021, and the second diversion section 1023 before flowing into the first solvent storage tank 105, which is mainly dimethyl carbonate.

[0122] Furthermore, when the internal temperature of the solvent extractor 100 is between 80 degrees Celsius and 100 degrees Celsius, the first valve 104 is closed, the second valve 106 is closed, and the third valve 108 is opened. The outflowing fraction flows through the first condenser 101, the guide section 1021, and the third diversion section 1024 before flowing into the second solvent storage tank 107. The fraction mainly consists of diethyl carbonate, ethylene carbonate, diethyl carbonate, and methyl ethyl carbonate.

[0123] Furthermore, the organic solvent in the first solvent storage tank 105 is dimethyl carbonate, which can be directly used as a leaching solvent; the organic solvent in the second solvent storage tank 107 can be separated into diethyl carbonate, propylene carbonate, ethylene carbonate, and methyl ethyl carbonate through negative pressure distillation.

[0124] Understandably, the above implementation scheme can prevent the decomposition of lithium hexafluorophosphate by staged heating, and also allow diethyl carbonate, which is the main component of the material, to converge to the first solvent storage tank 105 for reuse in the filtrate from the lithium battery leaching process. The material in the solvent extractor 100 is the electrolyte lithium hexafluorophosphate, and the remaining organic solvent in the solvent extractor 100 can prevent the filtrate from being overheated, which would lead to the decomposition of lithium hexafluorophosphate.

[0125] The absorption tank 103 provided in the embodiments of this application has a first output terminal 1031 and a second output terminal 1032. The device for full recycling of waste lithium battery electrolyte also includes a second condenser 110 and a hydrolysis reactor 111. One end of the second condenser 110 is connected to the first output terminal 1031, and the other end of the second condenser 110 is connected to the solvent extractor 100. The hydrolysis reactor 111 is connected to the absorption tank 103 through the second output terminal 1032, and the hydrolysis reactor 111 is connected to the solvent extractor 100.

[0126] It is understood that, through the above embodiments, the gas in the absorption tank 103 can be transported to the solvent extractor 100 after passing through the first output end 1031 and the second condenser 110, and the liquid in the absorption tank 103 can be transported to the hydrolysis reactor 111 through the second conveying end. In addition, the liquid in the solvent extractor 100 can be transported to the hydrolysis reactor 111.

[0127] In one embodiment, the liquid in the solvent extractor 100 is transferred to the hydrolysis reactor 111. Nitrogen gas is introduced into the reactor under a closed environment, and water, hydrochloric acid (concentration range of 1% to 2%), and tributyl phosphate are added. The hydrolysis reactor 111 includes a stirring device to ensure thorough stirring during the hydrolysis reaction. After the hydrolysis reactor 111 cools to room temperature and is depressurized to atmospheric pressure, solid lithium fluoride can be formed.

[0128] Furthermore, lithium hexafluorophosphate, water, and hydrochloric acid react to produce lithium fluoride, hydrogen fluoride, phosphoric acid, and other byproducts. Nitrogen can be used as an inert protective gas to prevent lithium hexafluorophosphate or the generated hydrogen fluoride from being oxidized by oxygen. Tributyl phosphate can be used as a solvent or extractant and can also promote the precipitation and separation of lithium fluoride.

[0129] The device for full recycling of waste lithium battery electrolyte provided in the embodiments of this application further includes: an electrolyte leaching device 112, which is connected to the solvent extractor 100. The electrolyte leaching device 112 is used to transport the filtrate to the solvent extractor 100, and the electrolyte leaching device 112 is connected to the first solvent storage tank 105.

[0130] Understandably, by providing the electrolyte leaching device 112, the disassembled and broken used lithium batteries and their electrolytes, as well as dimethyl carbonate solvent, can be contained, allowing the disassembled and broken used lithium batteries and their electrolytes to be jointly immersed in the dimethyl carbonate solvent, and the filtrate to be transported to the solvent extractor 100. In some embodiments, the electrolyte leaching device 112 can also perform ultrasonic leaching and filtration of the filtrate to improve the wetting efficiency of the filtrate and filter out impurities in the filtrate. Furthermore, the electrolyte leaching device 112 is connected to the first solvent storage tank 105, allowing the dimethyl carbonate in the first solvent storage tank 105 to flow back to the electrolyte leaching device 112 for immersing the disassembled and broken used lithium batteries and their electrolytes.

[0131] The device for full recycling of waste lithium battery electrolyte provided in the embodiments of this application further includes: a first filter element 113, an organic phase separator 114, and a primary fluoride extractor 115. The first filter element 113 is connected to the hydrolysis reactor 111. The interior of the first filter element 113 is divided into an upper filtrate layer and a lower sediment layer. The organic phase separator 114 has an inlet end 1141, a first outlet end 1142, and a second outlet end 1143. The inlet end 1141 is connected to the upper filtrate layer, the first outlet end 1142 is connected to the electrolyte leachator 112, and the primary fluoride extractor 115 is connected to the lower sediment layer.

[0132] Understandably, by setting the first filter element 113, the products in the hydrolysis reactor 111 can be filtered, solid lithium fluoride forms the lower precipitation zone, and other unprecipitated substances form the upper filtrate zone. By setting the organic phase separator 114, the aqueous phase and organic phase of the filtrate in the upper filtrate zone can be separated. The separated organic phase can be transported to the electrolyte leaching device 112 for recycling. By setting the primary fluoride extractor 115, the solid lithium fluoride in the lower precipitation zone can be collected.

[0133] In one embodiment, the volume of water used in the hydrolysis reactor 111 is between 20% and 30% of the volume of the reactor liquid; the volume of hydrochloric acid used is between 2% and 8% of the volume of the reactor liquid; and the mass ratio of tributyl phosphate to lithium hexafluorophosphate in the waste electrolyte is 0.005 to 0.01:1.

[0134] Furthermore, nitrogen gas is introduced into the internal pressure of the hydrolysis reactor 111 at a rate between 0.2 MPa and 0.5 MPa, the hydrolysis temperature is between 30 degrees Celsius and 50 degrees Celsius, and the hydrolysis time is between 30 minutes and 90 minutes.

[0135] Understandably, the solvent in the solvent extractor 100 contains a small amount of organic solvent and lithium hexafluorophosphate. The lithium hexafluorophosphate decomposes into lithium fluoride precipitate, phosphoric acid, and hydrogen fluoride. Hydrogen fluoride is essentially soluble in water under pressure. Tributyl phosphate can complex with phosphorus-containing substances, inhibiting their vaporization. The organic solvent separated by the organic separator undergoes extraction and layering, and can be refluxed to the electrolyte leaching unit 112.

[0136] The device for full recycling of waste lithium battery electrolyte provided in the embodiments of this application further includes: a phosphorus extractor 116, a second filter element 117, an impurity metal separator 118, a third filter element 119, a fourth filter element 120, a lithium extractor 121, a fifth filter element 122, a secondary fluorine extractor 123, and a sixth filter element 124. The phosphorus extractor 116 is connected to the second outlet end 1143, the second filter element 117 is connected to the hydrolysis reactor 111, the impurity metal separator 118 is connected to the second filter element 117, the third filter element 119 is connected to the impurity metal separator 118 and is connected to the primary fluorine extractor 115, the fourth filter element 120 is connected to the primary fluorine extractor 115, the lithium extractor 121 is connected to the fourth filter element 120, the fifth filter element 122 is connected to the lithium extractor 121, and the sixth filter element 124 is connected to the secondary fluorine extractor 123.

[0137] Understandably, by setting up the phosphorus extractor 116, phosphoric acid in the aqueous solvent can be reacted to generate a phosphorus-containing precipitate, thus recovering phosphorus from the aqueous solvent. By setting up the impurity metal separator 118, impurity metals can be removed from the aqueous solvent after phosphorus removal. By setting up the primary fluorine extractor 115, fluorine can be recovered from the aqueous solvent after impurity metal removal. By setting up the lithium extractor 121, lithium can be recovered from the aqueous solvent after fluorine recovery. By setting up the secondary fluorine extractor 123, fluorine can be recovered again from the aqueous solvent after lithium recovery. This allows for the complete recovery of organic solvents and high-value lithium, fluorine, and phosphorus elements from waste lithium battery electrolytes, while removing impurity metals from waste lithium batteries. By setting up the second filter element 117, the third filter element 119, the fourth filter element 120, the fifth filter element 122, and the sixth filter element 124, different impurities in the aqueous solvent can be filtered, achieving the filtration and separation of different precipitates and filtrates from different stages of the aqueous solvent.

[0138] In one embodiment, ferric chloride is added to the phosphorus extractor 116 and stirred for 20 to 40 minutes. The stirred solution is then conveyed to the second filter element 117. The solid separated by the second filter element 117 is ferric phosphate, and the filtrate separated by the second filter element 117 is conveyed to the impurity metal separator 118.

[0139] Furthermore, the amount of ferric chloride used is in a mass ratio of 1.1 to 1.3:1 with that of lithium hexafluorophosphate in the waste electrolyte.

[0140] It is understandable that, through the above-described implementation method, phosphoric acid can react with ferric chloride to form ferric phosphate precipitate.

[0141] It should be noted that used lithium batteries contain impurities such as nickel and cobalt.

[0142] In one embodiment, the impurity metal separator 118 adjusts the pH to 3 to 4 with a 5% sodium hydroxide solution, and slowly adds a 5% sodium carbonate solution until no precipitate is formed. The solution is then conveyed to a third filter 119 for separation to obtain carbonate solids containing impurity metals such as nickel and cobalt. The filtrate separated by the third filter 119 is then conveyed to a primary fluorine extractor 115.

[0143] It is understandable that, through the above implementation method, impurity metals such as nickel and cobalt, as well as excess ferric chloride, react with sodium carbonate solution to form metal carbonate precipitates.

[0144] Furthermore, acid can be used to dissolve and precipitate the metals, such as nickel, cobalt, and iron, in order to recycle and utilize them.

[0145] In one embodiment, a calcium hydroxide suspension with a mass fraction of 5% to 10% is added to the primary fluoride extractor 115, wherein the mass ratio of calcium hydroxide to lithium hexafluorophosphate in the waste electrolyte is 2.8 to 2.9:1. The pH is adjusted to 9 to 10 using a 5% sodium hydroxide solution, and the primary fluoride extractor 115 is heated to between 50°C and 70°C, with stirring for 60 to 90 minutes. The solid obtained after separation through the fourth filter element 120 is calcium fluoride, and the filtrate after filtration through the fourth filter element 120 is transferred to the lithium extractor 121.

[0146] Furthermore, the solid obtained after separation by the fourth filter element 120 is calcium fluoride. After washing away alkaline impurities with 5% hydrochloric acid solution and drying, calcium fluoride with a purity of over 98% is obtained. In addition, it can also be used for acid hydrolysis to prepare high-purity hydrogen fluoride.

[0147] It is understandable that by using the above-described method, adding an appropriate amount of calcium hydroxide and adjusting the pH with sodium hydroxide solution, solid lithium fluoride can be dissolved and fluorine can be precipitated without introducing excessive calcium, so as not to affect the purity of lithium carbonate during subsequent lithium extraction.

[0148] Furthermore, lithium fluoride reacts with calcium hydroxide to form soluble lithium hydroxide and insoluble calcium fluoride.

[0149] In one embodiment, carbon dioxide is introduced into the lithium extractor 121, and the reaction is maintained under pressure until no precipitate is produced. The lithium carbonate solid is obtained by filtration through the fifth filter element 122 and dried to obtain battery-grade lithium carbonate. The filtrate after filtration through the fifth filter element 122 is then transported to the secondary fluorine extractor 123.

[0150] Furthermore, the carbon dioxide charging pressure in the lithium extractor 121 is maintained at 0.2 MPa to 0.3 MPa, and the pressure is maintained at an internal temperature of 60 degrees Celsius to 80 degrees Celsius for 40 minutes to 120 minutes.

[0151] It is understandable that lithium carbonate can be extracted through the above-described implementation method.

[0152] In one embodiment, a calcium chloride solution with a mass fraction of 5% to 10% is added to the secondary fluoride extractor 123. The mass ratio of calcium chloride to lithium hexafluorophosphate in the waste electrolyte is 0.2-0.6:1. The pH is adjusted to 9-10 using a 5% sodium hydroxide solution, and the reaction is stirred for 30 to 60 minutes. The solid obtained after passing through the sixth filter element 124 is calcium fluoride.

[0153] It is understood that, through the above-described embodiments, the residual fluorine in the filtrate after lithium extraction can be effectively precipitated, so that the residual concentration of fluorine can be reduced to within 10 ppm.

[0154] like Figure 2 As shown, embodiments of this application provide a method for the complete recycling of waste lithium battery electrolyte, applied to the waste lithium battery electrolyte recycling apparatus provided in any of the above embodiments. The method includes the following steps:

[0155] S701: The filtrate from the lithium battery is delivered to the solvent extractor 100;

[0156] S702: Open the first valve 104 and close the second valve 106 to adjust the first condenser 101 to the first temperature so that the first part of the volume of filtrate passes through the first condenser 101, the guide section 1021 of the conveying member 102 and the first diversion section 1022 of the conveying member 102 in sequence and is conveyed to the absorption tank 103.

[0157] S703: Close the first valve 104 and open the second valve 106 to adjust the first condenser 101 to the second temperature so that the second part of the filtrate passes through the first condenser 101, the guide section 1021 and the second diversion section 1023 of the conveying member 102 in sequence and is conveyed to the first solvent storage tank 105.

[0158] It is understood that, through the above embodiments, the solvent extractor 100 can distill the filtrate of the lithium battery to separate the solvent, electrolyte, and decomposition products of the electrolyte in the filtrate. By setting the first condenser 101, the distilled fraction can be cooled. By setting the absorption tank 103, the distilled decomposition products phosphorus pentafluoride and hydrogen fluoride can be absorbed. By setting the first solvent storage tank 105, the distilled solvent can be stored. The electrolyte and residual substances in the filtrate will be stored in the solvent extractor 100. By setting the first valve 104 and the second valve 106, the direction of the distilled fraction can be controlled. When the first valve 104 is open and the second valve 106 is closed, the fraction can be transported to the absorption tank 103. When the first valve 104 is closed and the second valve 106 is open, the fraction can be transported to the first solvent storage tank 105.

[0159] Therefore, the device for the complete recycling of waste lithium battery electrolyte provided in the embodiments of this application can solve the problem of the waste of solvent and electrolyte resources caused by the inability to recycle the solvent and electrolyte in the electrolyte.

[0160] The method provided in the embodiments of this application, when opening the first valve 104 and closing the second valve 106, further includes: closing the third valve 108 of the waste lithium battery electrolyte full recycling device.

[0161] It is understood that, through the above implementation method, when the first condenser 101 is adjusted to the first temperature, the distillate flowing out of the first condenser 101 can only pass through the guide section 1021 and the first diversion section 1022 of the conveyor 102 and be conveyed to the absorption tank 103, thereby allowing the distillate to be conveyed into the absorption tank 103.

[0162] The method provided in the embodiments of this application, when closing the first valve 104 and opening the second valve 106, further includes: closing the third valve 108 of the waste lithium battery electrolyte full recycling device.

[0163] It is understood that, through the above implementation method, when the first condenser 101 is adjusted to the second temperature, the distillate flowing out of the first condenser 101 can only be transported to the first solvent storage tank 105 through the guide section 1021 and the second diversion section 1023 of the conveyor 102, thereby allowing the distillate to be transported into the first solvent storage tank 105.

[0164] The method for full recycling of waste lithium battery electrolyte provided in the embodiments of this application further includes the following steps:

[0165] Close the first valve 104, close the second valve 106, open the third valve 108, and adjust the first condenser 101 to the third temperature so that the third volume of filtrate passes sequentially through the first condenser 101, the guide section 1021 and the third diversion section 1024 of the conveying component 102, and is conveyed to the second solvent storage tank 107.

[0166] Understandably, the fraction flowing out of the first condenser 101 can pass through the third diversion section 1024 and the third valve 108 and enter the second solvent storage tank 107, thereby separating dimethyl carbonate from other components in the solvent.

[0167] The method for full recycling of waste lithium battery electrolyte provided in the embodiments of this application further includes the following steps:

[0168] The first portion of the filtrate in the absorption tank 103 is sequentially transported to the hydrolysis reactor 111 and the first filter element 113.

[0169] The filtrate in the upper filtrate layer of the first filter element 113 is transported to the organic phase separator 114, and the solids in the lower sedimentation layer of the first filter element 113 are transported to the primary fluoride extractor 115.

[0170] The aqueous phase in the filtrate of the organic phase separator 114 is transported to the phosphorus extractor 116, and the organic phase in the filtrate of the organic phase separator 114 is transported to the electrolyte leaching unit 112.

[0171] The liquid in the pot of phosphorus extractor 116 is sequentially passed through the second filter element 117, the impurity metal separator 118, the third filter element 119, the primary fluorine extractor 115, the fourth filter element 120, the lithium extractor 121, the fifth filter element 122, and the secondary fluorine extractor 123 before being conveyed to the sixth filter element 124.

[0172] It is understood that, through the above implementation method, lithium, fluorine and phosphorus elements can be completely recovered from the first part of the volume of filtrate in the absorption tank 103, and impurity metals in the first part of the volume of filtrate can be removed.

[0173] It should be noted that nitrogen gas is introduced into the hydrolysis reactor 111, and water, 1%-2% hydrochloric acid and tributyl phosphate are added. The volume of water is 20%-30% of the volume of the liquid in the reactor 111, and the volume of hydrochloric acid is 2%-8% of the volume of the liquid in the reactor 111. The mass ratio of tributyl phosphate to lithium hexafluorophosphate in the waste electrolyte is 0.005-0.01:1. The internal pressure of the hydrolysis reactor 111 is 0.2MPa-0.5MPa, the hydrolysis temperature is 30℃-50℃, and the hydrolysis time is 30min-90min.

[0174] Understandably, the solvent in the solvent extractor 100 contains a small amount of organic solvent and lithium hexafluorophosphate. The lithium hexafluorophosphate decomposes into lithium fluoride precipitate, phosphoric acid, and hydrogen fluoride. Hydrogen fluoride is essentially soluble in water under pressure. Tributyl phosphate can complex with phosphorus-containing substances, inhibiting their vaporization. The organic solvent separated by the organic separator undergoes extraction and layering, and can be refluxed to the electrolyte leaching unit 112.

[0175] It should be noted that ferric chloride is added to the phosphorus extractor 116, and the ratio of the amount of ferric chloride to the mass of lithium hexafluorophosphate in the waste electrolyte is 1.1~1.3:1.

[0176] It is understandable that, through the above-described implementation method, phosphoric acid can react with ferric chloride to form ferric phosphate precipitate.

[0177] It should be noted that the pH of the impurity metal separator 118 is adjusted to 3-4 with a 5% sodium hydroxide solution and a 5% sodium carbonate solution is added.

[0178] It is understandable that, through the above implementation method, impurity metals such as nickel and cobalt, as well as excess ferric chloride, react with sodium carbonate solution to form metal carbonate precipitates.

[0179] It should be noted that a 5%~10% mass fraction of calcium hydroxide suspension is added to the primary fluoride extractor 115. The mass ratio of calcium hydroxide to lithium hexafluorophosphate in the waste electrolyte is 2.8~2.9:1. The pH is adjusted to 9~10 by adding a 5% mass fraction of sodium hydroxide solution, the temperature is raised to 50℃~70℃, and the stirring reaction time is 60min~90min.

[0180] It is understandable that by using the above-described method, adding an appropriate amount of calcium hydroxide and adjusting the pH with sodium hydroxide solution, solid lithium fluoride can be dissolved and fluorine can be precipitated without introducing excessive calcium, so as not to affect the purity of lithium carbonate during subsequent lithium extraction.

[0181] It should be noted that carbon dioxide is filled into the lithium extractor 121 to maintain the internal pressure at 0.2 MPa to 0.3 MPa, and the pressure is maintained at an internal temperature of 60℃ to 80℃ for 40 min to 120 min.

[0182] It is understandable that lithium carbonate can be extracted through the above-described implementation method.

[0183] It should be noted that a 5%~10% mass fraction of calcium chloride solution is added to the secondary fluoride extractor 123. The mass ratio of calcium chloride to lithium hexafluorophosphate in the waste electrolyte is 0.2-0.6:1. The pH is adjusted to 9~10 by adding a 5% mass fraction of sodium hydroxide solution, and the reaction is stirred for 30min~60min.

[0184] It is understood that, through the above-described embodiments, the residual fluorine in the filtrate after lithium extraction can be effectively precipitated, so that the residual concentration of fluorine can be reduced to within 10 ppm.

[0185] The method for full recycling of waste lithium battery electrolyte provided in the embodiments of this application further includes the following steps:

[0186] The electrolyte in the electrolyte leaching unit 112 is transferred to the solvent extractor 100;

[0187] The second portion of the filtrate in the first solvent storage tank 105 is transported to the solvent extractor 100;

[0188] The gas in the absorption tank 103 is transported to the solvent extractor 100 after passing through the second condenser 110.

[0189] It is understood that through the above-described embodiments, organic solvents can be recovered, corrosive gases can be pre-separated, and dimethyl carbonate with high content can be collected and directly reused as leaching solvent in the solvent extractor 100.

[0190] In one embodiment, a method for the complete recycling of waste lithium battery electrolyte includes the following steps:

[0191] Step 1: The old lithium battery and dimethyl carbonate are transported to the electrolyte leaching device 112. After the old lithium battery is leached by dimethyl carbonate, a waste electrolyte liquid containing 8% lithium hexafluorophosphate is formed. 500 kg of this liquid is transported to the solvent extractor 100.

[0192] Step 2: The solvent extractor 100 is heated to 30 to 50 degrees Celsius. The first condenser 101 is set to a condensation temperature of 10 degrees Celsius. The first valve 104 is opened, the second valve 106 is closed, and the third valve 108 is closed. The distillate is fed into the absorption tank 103, where the phosphorus pentafluoride and hydrogen fluoride gases are absorbed by water. The insoluble matter in the absorption tank 103 is condensed by the second condenser 110 and returned to the solvent extractor 100. The liquid in the absorption tank 103 is transported to the hydrolysis reactor 111.

[0193] Step 3: After no more distillate flows out of the outlet of the first condenser 101, close the first valve 104, open the vacuum component 109, and maintain the vacuum degree inside the solvent extractor 100 at -0.095 MPa. Set the condensing temperature of the condenser 1 to -10 degrees Celsius. Heat the solvent extractor 100 to 70 degrees Celsius in stages and maintain it for 50 minutes. Open the second valve 106 and close the third valve 108. The outflowing distillate is fed into the first solvent storage tank 105. At this point, the distillate is 275 kg of dimethyl carbonate. Close the second valve 106 and open the third valve 108. Continue to heat to 90 degrees Celsius and maintain it for 20 minutes. Continue to heat to 120 degrees Celsius. During this period, the outflowing distillate is fed into the second solvent storage tank 107. At this point, the total distillate is 150 kg. Diethyl carbonate, ethylene carbonate, diethyl carbonate, and methyl ethyl carbonate can be further separated by negative pressure distillation. Subsequently, heating was stopped after observing that the liquid material in the solvent extractor 100 did not boil.

[0194] Step 4: The liquid in the solvent extractor 100 is transferred to the hydrolysis reactor 111. Nitrogen gas is introduced into the hydrolysis reactor 111 under a closed environment to a pressure of 0.3 MPa. 15 L of water, 2 L of 2% hydrochloric acid, and 0.5 kg of tributyl phosphate are added. The hydrolysis reactor 111 is set to a hydrolysis temperature of 40 degrees Celsius and a stirring hydrolysis time of 50 minutes. After the hydrolysis reactor 111 cools to room temperature, the pressure is released to atmospheric pressure. The solid is separated into lithium fluoride through the first filter element 113 and transferred to the primary fluorine extractor 115. The filtrate enters the organic phase separator 114. After extraction and separation, the aqueous phase is transferred to the phosphorus extractor 116, and the organic phase is dried and dehydrated before being returned to the electrolyte leaching unit 112.

[0195] Step 5: Add 46.8 kg of ferric chloride to the phosphorus extractor 116, wherein the mass ratio of ferric chloride to lithium hexafluorophosphate is 1.1:1, stir for 30 minutes, and then convey to the second filter element 117 to separate the solids. The filtrate is conveyed to the impurity metal separator 118, wherein the solid, after drying, is 38.8 kg of ferric phosphate.

[0196] Step Six: In the impurity metal separator 118, adjust the pH to 3 with a 5% sodium hydroxide solution, and slowly add a 5% sodium carbonate solution until no precipitate forms. The solution is then transferred to the third filter element 119 to separate the solid. The filtrate is transferred to the primary fluorine extractor 115. The solid is a carbonate of impurity metals such as nickel and cobalt, and excess iron. After drying, it weighs 7.5 kg and can be further dissolved in acid to extract the precipitate and then subjected to gradient extraction of nickel, cobalt, iron, and other metal elements.

[0197] Step 7: In the primary fluoride extractor 115, add 54.5 kg of a 10% (w / w) calcium hydroxide suspension. The mass ratio of calcium hydroxide to lithium hexafluorophosphate is 2.8:1. Adjust the pH to 9 using a 5% sodium hydroxide solution. Heat to 60°C and stir for 8 minutes. Separate the solid through the fourth filter element 120. Transfer the filtrate to the lithium extractor 121. After drying, the solid yields 57.1 kg of calcium fluoride with a purity of 98.5%.

[0198] Step 8: In lithium extractor 121, carbon dioxide is introduced to make the internal pressure of lithium extractor 121 0.2 MPa. The reaction is stirred until no precipitate is produced. The solid is filtered through the fifth filter element 122 and dried to obtain 18.9 kg of battery-grade lithium carbonate. The filtrate is sent to secondary fluorine extractor 123.

[0199] Step 9: In the secondary fluoride extractor 123, add a 10% (w / w) calcium chloride solution, with a calcium chloride content of 11.5 kg and a mass ratio of 0.4:1 with lithium hexafluorophosphate. Adjust the pH to 9 with a 5% sodium chloride solution, stir and react for 50 minutes. After passing through the sixth filter element 124, the solid obtained is calcium fluoride, which weighs 3.5 kg after drying. The residual fluorine concentration in the filtrate is 8 ppm.

[0200] It should be noted that the terms "one embodiment," "embodiment," "exemplary embodiment," "some embodiments," etc., mentioned in the specification indicate that the described embodiment may include a specific feature, structure, or characteristic, but not every embodiment necessarily includes that specific feature, structure, or characteristic. Furthermore, such phrases do not necessarily refer to the same embodiment. Moreover, when a specific feature, structure, or characteristic is described in connection with an embodiment, implementing such a feature, structure, or characteristic in conjunction with other embodiments, whether explicitly described or not, is within the knowledge scope of those skilled in the art.

[0201] Generally speaking, terms should be understood at least in part by their use in context. For example, at least in part by context, the term "one or more" as used in the text can be used to describe any feature, structure, or characteristic of the singular meaning, or a combination of features, structures, or characteristics of the plural meaning. Similarly, at least in part by context, terms such as "a" or "the" can also be understood to convey either singular or plural usage.

[0202] It should be readily understood that the terms “on,” “above,” and “on top of” in this application should be interpreted in the broadest possible sense, such that “on” means not only “directly on something” but also “on something” with an intermediate feature or layer therebetween, and that “above” or “on top of” means not only “on something” but also “on something” without an intermediate feature or layer therebetween (i.e., directly on something).

[0203] Furthermore, for ease of explanation, spatially relative terms such as "below," "below," "under," "above," and "above" may be used to describe the relationship of one element or feature relative to other elements or features as shown in the figures. Spatially relative terms are intended to encompass different orientations of the device in use or operation other than those shown in the figures. The device may have other orientations (rotated 90° or in other orientations), and the spatially relative descriptive terms used herein may be interpreted accordingly.

[0204] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A method for the complete recycling of waste lithium battery electrolyte, characterized in that, The method includes the following steps: The filtrate from the lithium battery is delivered to the solvent extractor (100). Open the first valve (104), close the second valve (106), and adjust the first condenser (101) to the first temperature so that the first part of the volume of the filtrate passes through the first condenser (101), the guide section (1021) of the conveyor (102), and the first diversion section (1022) of the conveyor (102) in sequence, and is conveyed to the absorption tank (103). Close the first valve (104), open the second valve (106), and adjust the first condenser (101) to the second temperature so that the second part of the filtrate passes through the first condenser (101), the guide section (1021), and the second diversion section (1023) of the conveying component (102) in sequence, and is conveyed to the first solvent storage tank (105). The first portion of the filtrate in the absorption tank (103) is sequentially transported to the hydrolysis reactor (111) and the first filter element (113). The filtrate in the upper filtrate layer of the first filter element (113) is transported to the organic phase separator (114), and the solids in the lower sedimentation layer of the first filter element (113) are transported to the primary fluoride extractor (115). The aqueous phase in the filtrate of the organic phase separator (114) is transported to the phosphorus extractor (116), and the organic phase in the filtrate of the organic phase separator (114) is transported to the electrolyte leaching unit (112). The liquid in the pot of the phosphorus extractor (116) is sequentially passed through the second filter (117), the impurity metal separator (118), the third filter (119), the primary fluorine extractor (115), the fourth filter (120), the lithium extractor (121), the fifth filter (122), and the secondary fluorine extractor (123) before being conveyed to the sixth filter (124). The liquid in the solvent extractor (100) is transported to the hydrolysis reactor (111). Nitrogen gas is introduced into the hydrolysis reactor (111), and water, 1%-2% hydrochloric acid and tributyl phosphate are added. The volume of water is 20%-30% of the volume of the liquid in the hydrolysis reactor (111), and the volume of hydrochloric acid is 2%-8% of the volume of the liquid in the hydrolysis reactor (111). The mass ratio of tributyl phosphate to lithium hexafluorophosphate in the waste electrolyte is 0.005-0.01:

1. The internal pressure of the hydrolysis reactor (111) is 0.2MPa-0.5MPa, the hydrolysis temperature is 30℃-50℃, and the hydrolysis time is 30min-90min.

2. The method for complete recycling of waste lithium battery electrolyte according to claim 1, characterized in that, When opening the first valve (104) and closing the second valve (106), the method further includes: Close the third valve (108) of the device for the complete recycling of waste lithium battery electrolyte.

3. The method for complete recycling of waste lithium battery electrolyte according to claim 1, characterized in that, When closing the first valve (104) and opening the second valve (106), the method further includes: Close the third valve (108) of the device for the complete recycling of waste lithium battery electrolyte.

4. The method for complete recycling of waste lithium battery electrolyte according to any one of claims 1-3, characterized in that, It also includes the following steps: Close the first valve (104), close the second valve (106), and open the third valve (108); adjust the first condenser (101) to the third temperature so that the third volume of the filtrate passes sequentially through the first condenser (101), the guide section (1021), and the third diversion section (1024) of the conveying component (102) and is conveyed to the second solvent storage tank (107).

5. The method for complete recycling of waste lithium battery electrolyte according to any one of claims 1-3, characterized in that, Ferric chloride is added to the phosphorus extractor (116), and the ratio of the amount of ferric chloride to the mass of lithium hexafluorophosphate in the waste electrolyte is 1.1~1.3:1; And / or, the pH of the impurity metal separator (118) is adjusted to 3-4 with a 5% sodium hydroxide solution and a 5% sodium carbonate solution is added. And / or, 5%~10% calcium hydroxide suspension is added to the primary fluoride extractor (115), the ratio of calcium hydroxide to lithium hexafluorophosphate in the waste electrolyte is 2.8~2.9:1, and the pH is adjusted to 9~10 by 5% sodium hydroxide solution, the temperature is raised to 50℃~70℃, and the stirring reaction time is 60min~90min; And / or, carbon dioxide is filled into the lithium extractor (121) to maintain the pressure inside the lithium extractor (121) at 0.2 MPa to 0.3 MPa, and the pressure is maintained at an internal temperature of 60°C to 80°C for 40 min to 120 min; And / or, 5%~10% calcium chloride solution is added to the secondary fluoride extractor (123), the ratio of calcium chloride to lithium hexafluorophosphate in the waste electrolyte is 0.2-0.6:1, the pH is adjusted to 9~10 by 5% sodium hydroxide solution, and the reaction is stirred for 30min~60min.

6. The method for complete recycling of waste lithium battery electrolyte according to any one of claims 1-3, characterized in that, It also includes the following steps: The electrolyte in the electrolyte leaching device (112) is transported to the solvent extractor (100). The second portion of the filtrate in the first solvent storage tank (105) is delivered to the solvent extractor (100). The gas in the absorption tank (103) is transported to the solvent extractor (100) after passing through the second condenser (110).

7. An apparatus for the complete recycling of waste lithium battery electrolyte, used to perform the method for the complete recycling of waste lithium battery electrolyte as described in any one of claims 1-6, characterized in that, The device for the complete recycling of waste lithium battery electrolyte includes: Solvent extractor (100) for containing the filtrate from the lithium battery; A first condenser (101) is connected to the solvent extractor (100). The conveying component (102) has a connected guide section (1021), a first diversion section (1022) and a second diversion section (1023), wherein the first diversion section (1022) and the second diversion section (1023) are arranged in parallel. An absorption tank (103) is connected to the first diversion section (1022). A first valve (104) is connected to the first diversion section (1022), and the first valve (104) is used to open or close the connection between the first diversion section (1022) and the absorption tank (103); A first solvent storage tank (105) is connected at one end to the second diversion section (1023), and at the other end to the solvent extractor (100). The second valve (106) is connected to the second diversion section (1023). The second valve (106) is used to open or close the connection between the second diversion section (1023) and the first solvent storage tank (105).

8. The apparatus for the complete recycling of waste lithium battery electrolyte according to claim 7, characterized in that, The conveying component (102) has a third diversion section (1024) that communicates with the guide section (1021), and the third diversion section (1024) is arranged in parallel with the first diversion section (1022); The device for the complete recycling of waste lithium battery electrolyte also includes: The second solvent storage tank (107) is connected to the third diversion section (1024). A third valve (108) is connected to the third diversion section (1024), and the third valve (108) is used to open or close the connection between the third diversion section (1024) and the second solvent storage tank (107); A vacuum element (109) is connected to the solvent extractor (100).

9. The apparatus for the complete recycling of waste lithium battery electrolyte according to claim 7 or 8, characterized in that, The absorption tank (103) has a first output end (1031) and a second output end (1032); The device for the complete recycling of waste lithium battery electrolyte also includes: The second condenser (110) has one end connected to the first output terminal (1031) and the other end connected to the solvent extractor (100). The hydrolysis reactor (111) is connected to the absorption tank (103) through the second output end (1032), and the hydrolysis reactor (111) is connected to the solvent extractor (100).

10. The apparatus for the complete recycling of waste lithium battery electrolyte according to claim 9, characterized in that, Also includes: An electrolyte leaching device (112) is connected to the solvent extractor (100) and is used to transport the filtrate to the solvent extractor (100); and the electrolyte leaching device (112) is connected to the first solvent storage tank (105).

11. The apparatus for the complete recycling of waste lithium battery electrolyte according to claim 10, characterized in that, Also includes: A first filter element (113) is connected to the hydrolysis reactor (111); the interior of the first filter element (113) is divided into an upper filtrate layer and a lower sediment layer; An organic phase separator (114) has an inlet end (1141), a first outlet end (1142), and a second outlet end (1143). The inlet end (1141) is connected to the upper filtrate layer, and the first outlet end (1142) is connected to the electrolyte leaching device (112). The primary fluoride extractor (115) is connected to the lower precipitate layer.

12. The apparatus for the complete recycling of waste lithium battery electrolyte according to claim 11, characterized in that, Also includes: Phosphorus extractor (116) is connected to the second liquid outlet (1143). The second filter element (117) is connected to the hydrolysis reactor (111). Impurity metal separator (118) is connected to the second filter element (117). The third filter element (119) is connected to the impurity metal separator (118) and is also connected to the primary fluorine extractor (115). The fourth filter element (120) is connected to the primary fluoride extractor (115). A lithium extractor (121) is connected to the fourth filter element (120). The fifth filter element (122) is connected to the lithium extractor (121). A secondary fluoride extractor (123) is connected to the fifth filter element (122). The sixth filter element (124) is connected to the secondary fluoride extractor (123).

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