CN114699794A - Electrolyte subcritical extraction recovery device and method of secondary battery - Google Patents
Electrolyte subcritical extraction recovery device and method of secondary battery Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 75
- 239000003792 electrolyte Substances 0.000 title claims abstract description 57
- 238000011084 recovery Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 31
- 238000003860 storage Methods 0.000 claims abstract description 14
- 239000012530 fluid Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000005086 pumping Methods 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000005553 drilling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003507 refrigerant Substances 0.000 claims description 3
- 238000005057 refrigeration Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 claims 1
- 239000000428 dust Substances 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000005191 phase separation Methods 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 9
- 159000000002 lithium salts Chemical class 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 238000000895 extractive distillation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0288—Applications, solvents
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The electrolyte subcritical extraction recovery device and method of the secondary battery, the recovery device and step mainly include: A. placing the battery into a dry pretreatment chamber, and opening a fluid passage for the battery; B. transferring the opened battery to an extraction high-pressure autoclave (HP) in a dry environment, closing an autoclave cover, pumping a liquid extraction medium in a subcritical state, wherein the working pressure P1 is between 0.5 and 7MPa, the temperature is between 0 and 60 ℃, and the extraction medium comprises nonflammable Freon solvents R22, R134a and the like; C. the extracted mixed solution enters a low-pressure separation kettle (LP) for phase separation, the working pressure P2 is between 0.15 and 3MPa, the temperature of the mixed solution is between 1 and 60 ℃, the Freon solvent is gasified and then enters a pipeline from the middle upper part of the separation kettle, the cooled mixed solution enters a circulating storage tank, and the electrolyte is discharged from the lower part of the separation kettle; D. an auxiliary extraction medium circulating storage tank and the like; the recovery device and the recovery method can efficiently, completely and environmentally extract and recover the electrolyte in the battery and safely recover other valuable materials in the battery.
Description
Technical Field
The invention belongs to the field of secondary batteries such as lithium ion or sodium ion batteries, and particularly relates to the field of battery recovery and resource recycling.
Background
Lithium ion batteries are widely applied to the fields of mobile phones, notebook computers, electric vehicles, energy storage and the like due to high energy density and no memory effect, the power batteries and the energy storage batteries which are fixedly used as mobile energy sources are large in usage amount at present, and a large number of batteries with service lives enter a recycling stage.
The current battery resource recycling method is, as described in documents CN113082781A, CN113745685A, CN113644333A, and the like, that after a circuit control board is removed from a battery pack, a battery cell is crushed at a low temperature under the protection of an inert gas, then an electrolyte in the crushed material is volatilized by heating, then a part of an ester solvent is recovered by condensation, the crushed material is continuously floated to separate out high-value active materials and current collector powder, and then elements such as Ni, Co, Cu, Al, and the like are recycled by a hydrometallurgy method; in this method, a lithium salt such as LiPF6 in the electrolyte is easily decomposed at high temperature such as frictional heat during crushing, and toxic gas such as PF5 or HF is released, thereby polluting the environment.
For the electrolyte recovery method and device in the battery, documents CN113394444A, CN212810388U, CN212683091U, etc. mention mechanical methods of cutting the battery case and recovering the electrolyte by pouring, centrifuging, or needling, because the electrolyte is retained in the micron-scale porous pores of the pole pieces of the battery pole group and the nanometer-scale porous pores of the diaphragm, under the retention action of capillary force, the traditional mechanical pouring, centrifuging, etc. methods can only recover a small amount of floating liquid, a large amount of electrolyte in the battery is not recovered, the effective recovery rate of the electrolyte is too low, and the value of the electrolyte is far from being excavated.
The document CN113314776A proposes that the recovered electrolyte is subjected to reduced pressure distillation at 100 ℃ and 130 ℃ to extract the ester solvent, and Na is adopted as the lithium salt in the distillation residue2CO3Continuously reacting to obtain LiCO3The method of (1) still has the problem of environmental protection treatment of toxic and harmful gases generated by thermal decomposition of lithium salt, and the document does not point out how to effectively recover the electrolyte from the waste batteries.
Document CN113471515A proposes a method for separating and extracting a chain-like or cyclic carbonate and a lithium salt in a recovered electrolyte by combining supercritical extractive distillation and molecular distillation, wherein the electrolyte is introduced into an extractive distillation tower, supercritical carbon dioxide or supercritical carbon dioxide plus an entrainer is introduced into the bottom of the extractive distillation tower for continuous countercurrent extraction, a gas phase after extractive distillation is discharged from the top of the tower, a liquid phase is discharged from the bottom of the tower, lithium salt solids are separated out after cooling, the pressure in an extraction kettle is 25-35MPa, the temperature is 40-50 ℃, and the entrainer adopts anhydrous methanol, anhydrous ethanol and ethyl butyl ketone; the pressure of the separation kettle is 6-8MPa, and the temperature is 50-55 ℃. The method does not relate to how to extract and recover the electrolyte from the waste battery, and only relates to an extraction and separation method for separating the recovered electrolyte from the ester solvent and the lithium salt, because the carbon dioxide supercritical extraction has selectivity and low extraction efficiency on the ester solvent and the macromolecular ester additive in the electrolyte, the process energy consumption is overlarge, and the method does not have economic practicability, and the supercritical carbon dioxide extraction process is not suitable for carrying out integral high-efficiency extraction and recovery on the electrolyte when the battery is recovered; in addition, excessive extraction pressure is a serious challenge for the open/close mode fatigue life of the autoclave, and equipment manufacturing and amortization costs are excessive.
The existing battery recovery technology has the disadvantages of environmental pollution, low recovery efficiency and serious resource waste; when the battery is cut and crushed, due to the existence of flammable and explosive electrolyte, short circuit heating and other reasons, the safety problems such as ignition and explosion and the like easily occur when the battery is recovered, so how to remove the flammable and explosive electrolyte before recovering other valuable materials in the battery is a difficult problem which needs to be solved urgently for the safe recovery of the battery; in addition, the prior art does not have a satisfactory solution in the aspect of recycling of high-value electrolyte in the battery; the invention is specially provided by combining the problems.
Disclosure of Invention
The invention provides a device and a method for economically, environmentally and efficiently recycling electrolyte in a battery and conveniently and safely recycling other valuable materials in the battery.
The electrolyte subcritical extraction recovery device and method of the secondary battery are characterized in that the electrolyte subcritical extraction recovery device mainly comprises: A. a pretreatment chamber (R1) with a dry environment, the relative humidity is controlled to be less than 1 percent, the dew point temperature is lower than-35 ℃, in order to prevent the lithium salt in the electrolyte from absorbing moisture in the air and decomposing, the battery is opened in the dry environment, a liquid extraction medium, a mixed liquid and a fluid passage used when the extraction medium is recovered after extraction are opened for the battery, the battery is put into an extraction autoclave to be kept in the dry environment when being opened and after being opened, more preferably, the relative humidity of the environment is controlled to be less than 0.8 percent, the dew point temperature is lower than-40 ℃, the environment temperature is between 11 ℃ and 25 ℃, and when the battery is opened, at least one part of the explosion-proof membrane is cut from the battery and a channel for preparing the fluid is removed; at least the kettle cover of the extraction high-pressure kettle is in a drying environment communicated with the pretreatment chamber when the kettle cover is opened or materials are loaded and unloaded; B. extracting high pressure autoclave (HP), putting the opened battery into the extracting high pressure autoclave, closing the cover, vacuumizing, injecting liquid extracting medium into the extracting high pressure autoclave (HP) by high pressure plunger pump, the liquid extracting medium entering into the autoclave is in subcritical state, the entering temperature of the liquid extracting medium is between 0 ℃ and 60 ℃, the working pressure P1 is between 0.5 and 7MPa, the liquid extracting medium comprises the following environment-friendly, non-flammable one or more compositions of Freon refrigerants which mainly contain Hydrochlorofluorocarbon (HCFC) or Hydrofluorocarbon (HFC): r134a, R22, R124, R125, R23, R410A, R408A, R409A, R507, R404A, R417A, R508A, R508B, R402AR, R402 BR; C. the liquid extraction method comprises the following steps that a single-stage or multi-stage series low-pressure separation kettle (LP) is adopted, the temperature of mixed liquid entering the LP and the temperature of a heat transfer medium of a heat exchanger or a jacket inside or outside the LP ranges from 1 ℃ to 60 ℃, the working pressure P2 is lower than P1, P2 ranges from 0.15 MPa to 3MPa, a single-stage or 2-4-stage series low-pressure separation kettle structure with step-by-step depressurization is adopted, liquid extraction medium is gasified, and electrolyte is effectively separated under the low pressure P2; D. the device comprises an attached extraction medium storage tank, a high-pressure plunger pump, a heat exchanger, a high-pressure valve, a connecting pipeline, a filter, a vacuum pump, a molecular sieve dehydration device, an electrolyte recovery storage tank and the like; the subcritical extraction and recovery method of the electrolyte of the secondary battery mainly comprises the following steps: step1, putting a battery pack or a single battery or a plurality of batteries into a tool, entering a pretreatment chamber (R1), mechanically punching or mechanically drilling one end or two ends of each battery or single battery of the battery pack or an explosion-proof membrane of the battery by adopting a mechanical method or laser or mechanically drilling holes, and preparing an inlet/outlet passage of a liquid extraction medium and a mixed solution; step2, transferring the opened battery pack or single battery into an extraction high-pressure autoclave (HP), closing the autoclave cover, pumping a Freon liquid extraction medium with the temperature of 0-60 ℃ and in a subcritical state into the extraction high-pressure autoclave (HP) by using a high-pressure plunger pump after vacuumizing, carrying out continuous flow extraction or intermittent flow extraction, and decompressing the formed mixed solution through a high-pressure valve and then entering a low-pressure separation kettle; step3, performing single-stage or 2-4-stage gradual pressure reduction type cascade separation on the extracted mixed solution in the low-pressure separation kettle, changing the Freon liquid extraction medium into a gas phase in the low-pressure separation kettle, discharging the gas phase from a pipeline connected with the middle upper part of the low-pressure separation kettle, continuously performing heat exchange and refrigeration, then entering an extraction medium storage tank for recycling, discharging the separated electrolyte from the lower part of the low-pressure separation kettle, and entering an electrolyte recovery storage tank for later use.
According to the subcritical extraction and recovery device and method for the electrolyte of the secondary battery, the high-pressure/low-temperature liquid Freon solvent which has good intersolubility with the electrolyte and is in a subcritical state is used as an extraction medium, the opening of the battery is provided with the pretreatment chamber in a dry environment, so that the lithium salt in the electrolyte can be prevented from absorbing water and decomposing, the Freon high-pressure/low-temperature liquid extraction medium in the subcritical state in the extraction autoclave and the electrolyte can be mutually dissolved, the phase separation is carried out in the low-pressure separation kettle, the process is carried out in a closed system, and the process is environment-friendly and efficient; the high-pressure liquid Freon solvent which is in a subcritical state and is close to room temperature can directly, efficiently and thoroughly dissolve/extract electrolyte from micro-pores of a battery electrode group and a diaphragm, and great safety and convenience are brought to subsequent continuous recovery and disposal of valuable positive and negative electrode active materials in the battery; the invention adopts a low-temperature extraction process at 0-60 ℃, prevents the battery from contacting moisture after opening, can effectively control the thermal decomposition of lithium salt, adopts a separation pressure of 0.15-3MPa, can utilize the high steam partial pressure of Freon at the same temperature, inhibits the volatilization of ester solvents in the electrolyte, obtains complete electrolyte components after the separation in the serially connected low-pressure separation kettles, has high purity, and can be used for the reproduction of the battery after the subsequent blending adjustment formula treatment such as molecular sieve dehydration.
The invention adopts a subcritical extraction process, and the working pressure design of the extraction high-pressure kettle is lower than 7MPa, so that the subcritical Freon solvent is used for dissolving the electrolyte, the manufacturing cost of pressure container equipment is reduced, the fatigue life of the pressure container can be greatly prolonged, and the recovery cost of the battery is reduced.
The subcritical extraction recovery device and the subcritical extraction recovery method have the advantages that the electrolyte is effectively recovered, and meanwhile, the safety and convenience and the recovery cost advantage which are not possessed by the conventional recovery method are brought to the whole recovery process of the battery.
In order to better understand the present invention, the following are some examples, and the apparatus and method for subcritical extraction and recovery of electrolyte of secondary battery according to the present invention can be variously combined and fine-tuned based on the spirit of the present invention.
Examples
Example 1: the electrolyte subcritical extraction recovery device and method of the secondary battery, the subcritical extraction recovery device mainly includes: A. a pretreatment chamber (R1) with a dry environment, the relative humidity is controlled to be less than 0.8%, the dew point temperature is lower than-40 ℃, the battery is opened in the dry environment, a liquid extraction medium, a mixed liquid and a fluid passage used when the extraction medium is recovered after extraction are opened for the battery, the battery is put into an extraction autoclave and kept in the dry environment when the battery is opened and after the battery is opened, the environmental temperature is between 15 ℃ and 25 ℃, in order to prevent short circuit when the battery is opened, the explosion-proof membrane is adsorbed by negative pressure, at least one part of the explosion-proof membrane is cut from the battery and is removed outwards, and a fluid channel is prepared; B. an extraction autoclave (HP) with a working pressure P1 of between 2.5 and 3.5MPa, a liquid extraction medium R22, a subcritical state and an entry temperature of between 30 and 40 ℃; C. working pressure P2 is between 1.0-1.8MPa, temperature of the mixture is between 35 ℃ and 45 ℃, and 2-stage low-pressure separation kettles (LP) are connected in series; C. the device comprises an attached extraction medium storage tank, a high-pressure plunger pump, a heat exchanger, a high-pressure valve, a connecting pipeline, a filter, a water cooling unit, a vacuum pump, a molecular sieve dehydration device and an electrolyte recovery storage tank; the subcritical extraction and recovery method of the electrolyte of the secondary battery mainly comprises the following steps: step1, placing the battery pack or a plurality of batteries with the circuit control board removed into a tool, vacuumizing the transition chamber, then entering a dry pretreatment chamber (R1), adsorbing an explosion-proof film at least one end of the battery pack or the single battery by adopting negative pressure, cutting an opening, removing the opening, and preparing a fluid passage; step2, transferring the battery pack or the batteries after opening to an extraction high-pressure autoclave (HP), vacuumizing, pumping a liquid extraction medium R22 preheated to 30-35 ℃ and in a subcritical state into the extraction high-pressure autoclave (HP) by using a high-pressure plunger pump, and carrying out continuous flow extraction for 2 hours; step3, heating the extracted mixed liquid to 35-40 ℃ by a heat exchanger, then feeding the mixed liquid into a low-pressure separation kettle, carrying out 2-stage cascade separation, discharging the R22 refrigerant into a gas phase in the low-pressure separation kettle from a pipeline connected with the upper part of the low-pressure separation kettle, continuously carrying out heat exchange and refrigeration, feeding the gas phase into an extraction medium storage tank for recycling, discharging the separated electrolyte from the lower part of the low-pressure separation kettle, and dehydrating the separated electrolyte by a subsequent series-connected molecular sieve to enter an electrolyte recovery storage tank.
Claims (2)
1. The subcritical extraction recovery device and method of electrolyte of the secondary battery, characterized by that, the subcritical extraction recovery device of electrolyte mainly includes: A. a pretreatment chamber (R1) having a dry environment, wherein the relative humidity is controlled to be less than 1%, the dew point temperature is lower than-35 ℃, the battery is opened therein, a liquid extraction medium and mixed liquid are opened for the battery, and a fluid passage used when the extraction medium is recovered after extraction, and at least a kettle cover of the extraction autoclave and the kettle cover are opened or materials are loaded and unloaded, and are in the dry environment communicated with the pretreatment chamber; B. extracting high pressure autoclave (HP), putting the opened battery into the extracting high pressure autoclave, closing the cover, vacuumizing, injecting liquid extracting medium into the extracting high pressure autoclave (HP) by a high pressure plunger pump, wherein the liquid extracting medium entering the extracting high pressure autoclave (HP) is in a subcritical state, the entering temperature of the liquid extracting medium is between 0 and 60 ℃, the working pressure P1 is between 0.5 and 7MPa, and the liquid extracting medium comprises the following environment-friendly and non-flammable composition of one or more Freon refrigerants which mainly contains hydrogen-containing chlorofluorocarbon (HCFC) or hydrogen-containing fluorocarbon (HFC): r134a, R22, R124, R125, R23, R410A, R408A, R409A, R507, R404A, R417A, R508A, R508B, R402AR, R402 BR; C. the temperature of the mixed liquid entering the low-pressure separation kettle (LP) is between 1 and 60 ℃, the working pressure P2 is lower than P1, P2 is between 0.15 and 3MPa, a single-stage or 2-4-stage multi-stage series low-pressure separation kettle structure with gradual depressurization is adopted, and the liquid extraction medium is gasified and effectively separated from the electrolyte under the low pressure P2; D. the device comprises an attached extraction medium storage tank, a high-pressure plunger pump, a heat exchanger, a high-pressure valve, a connecting pipeline, a dust filter, a vacuum pump, a molecular sieve dehydration device, an electrolyte recovery storage tank and the like; the subcritical extraction and recovery method of the electrolyte of the secondary battery mainly comprises the following steps: step1, putting a battery pack or a single battery or a plurality of batteries into a tool, entering a pretreatment chamber (R1), mechanically drilling or mechanically cutting one end or two ends of each battery or single battery of the battery pack or an explosion-proof membrane of the battery to prepare an inlet/outlet passage for liquid extraction medium and mixed liquid; step2, transferring the opened battery pack or single battery into an extraction autoclave (HP), closing a kettle cover, pumping a Freon liquid extraction medium with the temperature of 0-60 ℃ and in a subcritical state into the extraction autoclave (HP) by using a high-pressure plunger pump after vacuumizing, carrying out continuous flow extraction or intermittent flow extraction, and decompressing the formed mixed solution through a high-pressure valve and then entering a low-pressure separation kettle; step3, performing single-stage or 2-4-stage gradual pressure reduction type cascade separation on the extracted mixed solution in the low-pressure separation kettle, changing the Freon liquid extraction medium into a gas phase in the low-pressure separation kettle, discharging the gas phase from a pipeline connected with the middle upper part of the low-pressure separation kettle, continuously performing heat exchange and refrigeration, then entering an extraction medium storage tank for recycling, discharging the separated electrolyte from the lower part of the low-pressure separation kettle, and entering an electrolyte recovery storage tank for later use.
2. The apparatus and method for subcritical extraction and recovery of electrolyte of secondary battery according to claim 1, characterized in that, the cell is maintained in a pretreatment chamber (R1) environment with dry environment both when opened and after opened, the relative humidity is controlled to be less than 0.8%, the dew point temperature is lower than-40 ℃, the environment temperature is between 11 ℃ and 25 ℃, the cell is opened preferably by sucking the rupture membrane with negative pressure, and at least a part of the rupture membrane is cut and removed from the cell to prepare a fluid channel.
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