CN114204129B - Method for recycling agglomeration or plate jelly formed in positive electrode gel preparation process - Google Patents
Method for recycling agglomeration or plate jelly formed in positive electrode gel preparation process Download PDFInfo
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- CN114204129B CN114204129B CN202111463295.2A CN202111463295A CN114204129B CN 114204129 B CN114204129 B CN 114204129B CN 202111463295 A CN202111463295 A CN 202111463295A CN 114204129 B CN114204129 B CN 114204129B
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- 238000000034 method Methods 0.000 title claims abstract description 58
- 235000015110 jellies Nutrition 0.000 title claims abstract description 34
- 239000008274 jelly Substances 0.000 title claims abstract description 34
- 239000000499 gel Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title claims abstract description 13
- 238000005054 agglomeration Methods 0.000 title abstract description 14
- 230000002776 aggregation Effects 0.000 title abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 239000002033 PVDF binder Substances 0.000 claims abstract description 30
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 30
- 239000003292 glue Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims 1
- 239000002003 electrode paste Substances 0.000 claims 1
- 238000004537 pulping Methods 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention provides a method for recycling a gel formed in a positive electrode gel preparation process, which comprises the following steps: (1) Crushing the jelly formed in the positive electrode gel preparation process to obtain small jelly; (2) Mixing small jelly with NMP and alcohol regulator, stirring and dispersing to obtain a gel; (3) The invention solves the waste problem caused by PVDF agglomeration or hardening in the process of preparing glue, and the recovered agglomeration or hardening glue can be directly prepared into glue with NMP and PVDF for use in the pulping process.
Description
Technical Field
The invention belongs to the technical field of battery materials, and relates to a method for recycling an agglomeration or plate jelly formed in a positive electrode gel preparation process.
Background
In the process of stirring and pulping in the preparation process of the ternary lithium ion battery positive plate, a glue solution prepared from N-methyl pyrrolidone (NMP) and polyvinylidene fluoride (PVDF) is required, the glue preparation process and the pulping process are usually separated for the convenience and efficiency of the pulping process, the solid content, viscosity, appearance and other properties of the glue solution have great influence on the pulping effect, and the quality of the glue solution directly influences the electrical property of the ternary lithium battery. In the mass continuous glue making process, a continuous automatic feeding system is adopted in a factory, PVDF with a certain mass is put into NMP, and PVDF is dissolved through stirring and dispersing processes to prepare glue solution for pulping.
In the continuous automatic glue making process, aggregates are often formed on the inner wall and the bottom of the glue making tank, the stirring paddles, the dispersing disc, the feeding port and the inner wall of the glue making tank cover by PVDF due to uneven dispersion and stirring, and a plate-shaped jelly is seriously formed, so that the glue making tank needs to be cleaned regularly. These cleaned agglomerates and plate-like gums are often disposed of as waste refuse, which results in a significant waste of resources.
CN111100324a discloses a method and a device for recovering PVDF as a binder of waste lithium battery, which are characterized in that after the battery core of the waste lithium battery is crushed and placed into a dissolution container containing an organic solvent and provided with a stirrer, PVDF as a binder is dissolved in the organic solvent, then a movable plate arranged in the dissolution container is opened to place the organic solvent containing PVDF into a filtration container for filtration, filtrate is introduced into a preheating device for preheating by a centrifugal pump and then is introduced into a vacuum distillation tower for vacuum distillation, so that PVDF as a binder of waste lithium battery is obtained, other metal ions are introduced in the process of immersing fragments of the waste battery core, and the steel shell of the waste lithium battery may rust due to long service time, rust may fall into the battery core in the process of disassembly, and the obtained PVDF has poor direct application effect.
CN111710932a discloses a method for recovering the positive electrode adhesive of the retired lithium ion battery, which comprises the steps of firstly immersing the positive electrode powder of the retired lithium ion battery in an organic mixed solvent, then placing the organic mixed solvent in a reaction kettle, mechanically stirring to fully dissolve the adhesive, separating the positive electrode powder and the organic solution containing PVDF by using a centrifuge, separating and recovering the organic mixed solvent and PVDF by using a vacuum rotary evaporation evaporator, wherein the recovered PVDF cannot be applied in diameter.
The PVDF recycling method provided by the scheme has the problems that the purity of the recycled PVDF is low and the recycled PVDF cannot be directly utilized, so that the PVDF recycling method which is simple and has high purity of the recycled PVDF and can be directly utilized is very necessary to develop.
Disclosure of Invention
The invention aims to provide a method for recycling an agglomeration or plate-like jelly formed in a positive electrode gel preparation process, which solves the problem of waste caused by agglomeration or plate-like jelly of PVDF in the gel preparation process, and the recycled agglomeration or plate-like jelly can be directly prepared into a gel solution with NMP and PVDF for a pulping process.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a method for recycling an agglomeration or plate jelly formed in a positive electrode gel preparation process, which comprises the following steps:
(1) Crushing the jelly formed in the positive electrode gel preparation process to obtain small jelly;
(2) Mixing small jelly with NMP and alcohol regulator, stirring and dispersing to obtain a gel;
(3) Adjusting the solid content of the glue solution, and obtaining the glue solution for standby through filtering treatment and iron removal treatment.
The invention adopts a simple method to recycle the agglomeration or plate jelly formed in the positive electrode gel preparation process to prepare the gel, the content of other impurity ions in the gel is low, the purity of the binder is high, the method has simple flow, and the obtained gel can be directly used in the pulping process.
Preferably, the mass of the small gel is m1, the mass of NMP is m2, and the mass of the alcohol additive is m3.
Preferably, the m1 and m2 satisfy the relation: 5% or less m 1/(m1+m2) or less 8%, for example: 5%, 5.5%, 6%, 6.5%, 7% or 8%, etc., preferably m 1/(m1+m2) =6.
Preferably, the m1, m2 and m3 satisfy the relation: 0.1% or less m 3/(m1+m2+m3) or less 1%, for example: 0.1%, 0.3%, 0.5%, 0.7% or 1%, etc., preferably m 3/(m1+m2+m3) =0.5%.
Preferably, the size of the small jelly in the step (1) is 0.1-10 cm 2 For example: 0.1cm 2 、0.5cm 2 、1cm 2 、2cm 2 、5cm 2 、8cm 2 Or 10cm 2 Etc.
Preferably, the alcohol modifier of step (2) comprises any one or a combination of at least two of ethanol, propanol, butanol or n-propanol, preferably n-propanol.
Preferably, the temperature of the stirring and dispersing in step (2) is 40 to 70 ℃, for example: 40 ℃, 45 ℃, 50 ℃, 60 ℃ or 70 ℃ and the like.
Preferably, the vacuum degree of stirring and dispersing is less than or equal to-80 Kpa.
Preferably, the stirring in step (2) is carried out at a speed of 20 to 30rpm, for example: 20rpm, 22rpm, 25rpm, 28rpm or 30rpm, etc.
Preferably, the stirring time is 1 to 2 hours, for example: 1h, 1.2h, 1.5h, 1.8h, 2h, etc.
Preferably, the speed of the dispersion in step (2) is 1000 to 1300rpm, for example: 1000rpm, 1050rpm, 1100rpm, 1200rpm, 1300rpm, or the like.
Preferably, the dispersing time is 2 to 3 hours, for example: 2h, 2.2h, 2.5h, 2.8h or 3h, etc.
Preferably, the method for adjusting the solid content of the glue solution in the step (3) is adding NMP or PVDF.
Preferably, the glue solution is stirred and dispersed after the solid content of the glue solution is regulated.
Preferably, the stirring and dispersing time is 1 to 2 hours, for example: 1h, 1.2h, 1.5h, 1.8h, 2h, etc.
Preferably, the filter mesh number of the filtering treatment in the step (3) is 200-400 mesh, for example: 200 mesh, 220 mesh, 250 mesh, 300 mesh or 400 mesh, etc.
Preferably, the apparatus for iron removal treatment in step (3) includes an iron remover.
Preferably, the iron remover is made of stainless steel.
Compared with the prior art, the invention has the following beneficial effects:
the method is used for recycling the agglomeration or plate-like jelly formed in the positive electrode gel preparation process by a simple method, and preparing the gel, so that the prepared gel has high purity, the effect is similar to that of the binder gel prepared by the conventional method, and the recycling of the waste agglomeration-like and plate-like PVDF in the gel preparation process is realized, and the method is low in cost and environment-friendly.
Drawings
FIG. 1 is a graph showing the 24-hour viscosity change of a dope-prepared slurry obtained by the recovery method described in example 1.
FIG. 2 is a graph showing the 24-hour viscosity change of a slurry produced normally by continuously producing a dope as described in comparative example 1.
Fig. 3 is a comparative graph of the coating adhesion test after the dope of example 1 and comparative example 1 is made into a paste, A1, A2 and A3 are bar graphs of the coating adhesion test of the dope of example 1 and comparative example 1 on the front surface of an aluminum foil three times, and B1, B2 and B3 are bar graphs of the coating adhesion test of the dope of example 1 and comparative example 1 on the back surface of an aluminum foil three times.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a method for recycling an agglomeration or plate jelly formed in a positive electrode gel preparation process, which comprises the following steps:
(1) Cutting the collected agglomerated or plate-like jelly into 6cm in size with ceramic knife 2 Weighing 55kg of the mass, putting the mass into a stainless steel stirring tank with 1000L of volume, adding 850kg of N-methylpyrrolidone (NMP) and 5.02kg of N-propanol into the stainless steel stirring tank, setting the temperature of the stirring tank to 50 ℃, setting the vacuum degree to-80 kPa, setting the stirring speed to 25rpm, setting the dispersion speed to 1200rpm, and stirring and dispersing for 4 hours, wherein m 1/(m1+m2) =6%, and m 3/(m1+m2+m3) =0.55%;
(2) Stopping dispersing, cooling to 23 ℃, breaking vacuum, sampling and detecting the solid content of the glue solution, wherein the measured value is 5.13%;
(3) Adding 8.33kg of PVDF powder, setting the temperature of a stirring tank to 50 ℃, setting the vacuum degree to-80 kPa, setting the dispersion speed to 1200rpm, stirring and dispersing for 2 hours, stopping dispersing, cooling to 23 ℃, breaking vacuum, sampling and detecting the solid content of the glue solution, wherein the measured value is 6.25%, the solid content meets the production requirement, and the glue solution is transported through a 300-mesh filter and an iron remover to a storage tank by a diaphragm pump and is used in the pulping process.
Example 2
The embodiment provides a method for recycling an agglomeration or plate jelly formed in a positive electrode gel preparation process, which comprises the following steps:
(1) Cutting the collected agglomerate or plate-like jelly into 8cm in size with ceramic knife 2 Weighing 60kg of the mass, putting the small blocks into a stainless steel stirring tank with 1000L of volume, adding 800kg of N-methylpyrrolidone (NMP) and 5kg of N-propanol into the stainless steel stirring tank, setting the temperature of the stirring tank to 50 ℃, setting the vacuum degree to-80 kPa, setting the stirring speed to 25rpm, setting the dispersion speed to 1200rpm, and stirring and dispersing for 4h, wherein m 1/(m1+m2) =7%, and m 3/(m1+m2+m3) =0.58%;
(2) Stopping dispersing, cooling to 23 ℃, breaking vacuum, sampling and detecting the solid content of the glue solution, wherein the measured value is 5.25%;
(3) 7.56kg PVDF powder is added, the temperature of a stirring tank is set to be 50 ℃, the vacuum degree is set to be-80 kPa, the dispersion speed is 1200rpm, stirring and dispersing are carried out for 2 hours, dispersing is stopped, cooling is carried out to 23 ℃, vacuum breaking is carried out, the solid content of the glue solution is detected by sampling, the measured value is 6.25%, the solid content meets the production requirement, and the glue solution is transported through a 300-mesh filter and an iron remover to a storage tank through a diaphragm pump and is used in the pulping process.
Example 3
This example differs from example 1 only in that the NMP described in step (1) has a mass of 600kg, and the other conditions and parameters are exactly the same as example 1, m 1/(m1+m2) =8.3%.
Example 4
This example differs from example 1 only in that the NMP described in step (1) has a mass of 1050kg, and the other conditions and parameters are exactly the same as in example 1, m 1/(m1+m2) =4.9%.
Example 5
This example differs from example 1 only in that the mass of n-propanol described in step (1) is 10kg, and the other conditions and parameters are exactly the same as example 1, m 3/(m1+m2+m3) =1.1%.
Example 6
This example differs from example 1 only in that the mass of n-propanol described in step (1) is 0.8kg, and the other conditions and parameters are exactly the same as in example 1, m 3/(m1+m2+m3) =0.088%.
Comparative example 1
This comparative example differs from example 1 only in that the agglomerated or plate-like jelly of step (1) was replaced with PVDF powder, and the other conditions and parameters were exactly the same as in example 1.
Performance test:
the glue solution obtained in the examples 1-6 and the comparative example 1 is mixed with NCM523, NCM811, conductive carbon SP, conductive carbon KS-6 and NMP according to a certain mass proportion, and the mixture is subjected to procedures of powder dry mixing, pre-kneading, stirring, dispersing and the like to obtain slurry, wherein the stirring speed is 15rpm, the dispersing speed is 9000rpm, the powder dry mixing temperature is less than or equal to 45 ℃, the dispersing temperature is less than or equal to 60 ℃, the cooling water temperature is 15 ℃, the obtained slurry is transported through a 300-mesh filter by a diaphragm pump, an iron remover is transferred into a 600L transfer tank, the storage tank is provided with a motor stirring and vacuum system, the stirring speed of the motor is 20-30rpm, the vacuumizing defoaming time is not less than 60 minutes, the slurry in the 600L transfer tank is transported through a 300-mesh filter by the diaphragm pump, the iron remover is transferred into a 60L storage tank by a screw pump to be transferred into an extrusion type coating die head for coating, the coated pole piece is subjected to the procedures of drying, rolling, slitting, winding, assembling, cleaning, liquid injection, formation, normal temperature standing and the like to obtain a 18650 cylindrical battery, the theoretical capacity of the battery is 2500mAh, the voltage is 3V, the discharge cut-off voltage is 2.5V, the charging temperature is 0-60 ℃, the discharging temperature is-20-80 ℃, the battery is discharged to 2.5V at room temperature (25 ℃), the battery is placed for 10min, then is charged to 4.2V at constant current and constant voltage, the charging is stopped when the charging current is reduced to 0.1A, the charging is stopped for 10min after the charging, then is discharged to 2.5V at 10A current respectively, the cut-off temperature is set at 75 ℃, the battery is placed for 30min, the steps are repeated for 200 weeks, a cycle number-energy retention rate curve is drawn, the cycle is tested for 200 weeks, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the method of the present invention for recovering the agglomerated or plate-like jelly according to examples 1 to 6 and comparative example 1 provides a slurry having a stable viscosity and a stable solid content, and a small fluctuation range, and a capacity retention rate of 93.6% or more after 200 weeks of the cycle under the battery 10A.
As can be seen from the comparison of examples 1 and examples 3 to 4, the addition amount of NMP in the step (1) affects the effect of recovering the jelly, the relation between the mass (m 2) of NMP and the mass (m 1) of the jelly is controlled to be 5% -m 1/(m1+m2) 8%, the effect of recovering the jelly is good, and if the addition amount of NMP is beyond the range, the effect of preparing the slurry is reduced to different degrees.
As can be seen from the comparison of examples 1 and examples 5 to 6, the addition amount of the alcohol additive in the step (1) affects the effect of recovering the jelly, the relation between the mass (m 3) of the alcohol additive and the mass (m 1) of the jelly and the mass (m 2) of NMP is controlled to be 0.1% or less and less than or equal to m 3/(m1+m2+m3) or less and 1%, the effect of recovering the jelly is good, and if the addition amount exceeds the range, the effect after the slurry is prepared is reduced to different degrees.
After the glue solutions obtained in example 1 and comparative example 1 were prepared into slurries, the viscosity changes of the slurries were measured for 24 hours, the test results of example 1 are shown in fig. 1, the test results of comparative example 1 are shown in fig. 2, the slurries obtained in example 1 and comparative example 1 were subjected to a coating adhesion test, the coating adhesion test chart is shown in fig. 3, the coating mode is extrusion type double-sided coating, wherein A1-A3 is the peeling force measured by coating on the smooth surface of an aluminum foil, and B1-B3 is the peeling force measured by coating on the rough surface of an aluminum foil, and the test method is referred to GB/T2791-1995.
The method is characterized in that the agglomeration or plate-like jelly formed in the positive electrode gel preparation process is recovered by a simple method, the prepared gel is high in purity and similar to the adhesive gel prepared by a conventional method in effect, and the recovery and reutilization of the waste agglomeration-like and plate-like PVDF in the gel preparation process are realized, so that the method is low in cost and environment-friendly.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (16)
1. A method for recycling an agglomerated or plate jelly formed during a positive electrode paste process, the method comprising the steps of:
(1) Crushing the jelly formed in the positive electrode gel preparation process to obtain small jelly;
(2) Mixing small jelly with NMP and alcohol regulator, stirring and dispersing to obtain a gel;
(3) Adjusting the solid content of the glue solution, and obtaining the glue solution to be used through filtering treatment and iron removal treatment;
the mass of the small colloid is calculated as m1, the mass of NMP is calculated as m2, the mass of the alcohol regulator is calculated as m3, and the m1 and m2 satisfy the relation: m 1/(m1+m2) is more than or equal to 5% and less than or equal to 8%, and the m1, m2 and m3 satisfy the relation: and the gum comprises agglomerate or plate PVDF, wherein m < 3 >/(m1+m2+m3) is more than or equal to 0.1% and less than or equal to 1%.
2. The method of claim 1, wherein the small pieces of gum of step (1) have a size of 0.1 to 10cm 2 。
3. The method of claim 1, wherein the alcohol modifier of step (2) comprises any one or a combination of at least two of ethanol, propanol, butanol, or n-propanol.
4. The method of claim 1, wherein the temperature of stirring and dispersing in step (2) is 40 to 70 ℃.
5. The method of claim 1, wherein the stirring and dispersing vacuum is less than or equal to-80 Kpa.
6. The method of claim 1, wherein the stirring in step (2) is at a speed of 20 to 30rpm.
7. The method of claim 6, wherein the stirring is for a period of 1 to 2 hours.
8. The method of claim 1, wherein the speed of dispersion in step (2) is 1000 to 1300rpm.
9. The method of claim 8, wherein the dispersing is for a period of 2 to 3 hours.
10. The method of claim 1, wherein the method of adjusting the solids content of the dope of step (3) is adding NMP or PVDF.
11. The method of claim 10, wherein the glue solution is stirred and dispersed after the solids content is adjusted.
12. The method of claim 11, wherein the stirring and dispersing time is 1 to 2 hours.
13. The method of claim 1, wherein the filter mesh size of the filtering treatment of step (3) is 200-400 mesh.
14. The method of claim 13, wherein the filter is stainless steel.
15. The method of claim 1, wherein the means for iron removal treatment of step (3) comprises an iron remover.
16. The method of claim 15, wherein the iron remover is stainless steel.
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| WO2008034295A1 (en) * | 2006-09-19 | 2008-03-27 | Shenzhen Bak Battery Co., Ltd | A lithium ion battery electrode plate,a lithium ion battery electrode core and the preparation method of the same |
| KR101648693B1 (en) * | 2016-03-18 | 2016-09-22 | 주식회사 피엠알 | Valuable metals recovery system from the waste slurry of lithium secondary battery |
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| JP2005166331A (en) * | 2003-12-01 | 2005-06-23 | Shin Kobe Electric Mach Co Ltd | Manufacturing method of lithium ion secondary battery |
| CN111100324A (en) * | 2019-12-31 | 2020-05-05 | 陕西科技大学 | Method and device for recovering waste lithium battery binder PVDF |
| CN111564631B (en) * | 2020-03-27 | 2021-08-31 | 惠州市恒泰科技股份有限公司 | Lithium ion battery positive glue solution and preparation method thereof |
| CN111933891A (en) * | 2020-07-27 | 2020-11-13 | 海口安博尔能源技术开发有限公司 | Battery pole piece and processing method thereof |
| CN111710932A (en) * | 2020-08-11 | 2020-09-25 | 湖南省正源储能材料与器件研究所 | Method for recovering binder of retired lithium ion battery anode |
| CN112246835B (en) * | 2020-10-04 | 2022-03-04 | 湖南金源新材料股份有限公司 | Method for disassembling and separating waste lithium ion batteries |
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| WO2008034295A1 (en) * | 2006-09-19 | 2008-03-27 | Shenzhen Bak Battery Co., Ltd | A lithium ion battery electrode plate,a lithium ion battery electrode core and the preparation method of the same |
| KR101648693B1 (en) * | 2016-03-18 | 2016-09-22 | 주식회사 피엠알 | Valuable metals recovery system from the waste slurry of lithium secondary battery |
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