CN110391474A - A kind of charging method of waste and old lithium ion battery - Google Patents
A kind of charging method of waste and old lithium ion battery Download PDFInfo
- Publication number
- CN110391474A CN110391474A CN201810370965.8A CN201810370965A CN110391474A CN 110391474 A CN110391474 A CN 110391474A CN 201810370965 A CN201810370965 A CN 201810370965A CN 110391474 A CN110391474 A CN 110391474A
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- China
- Prior art keywords
- waste
- lithium ion
- battery
- ion battery
- salt
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- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000002699 waste material Substances 0.000 title claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 61
- 150000003839 salts Chemical class 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 230000005611 electricity Effects 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000004020 conductor Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229920000767 polyaniline Polymers 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims 1
- 229920000128 polypyrrole Polymers 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 10
- 238000009938 salting Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 6
- 208000028659 discharge Diseases 0.000 description 94
- 230000000694 effects Effects 0.000 description 21
- 238000001514 detection method Methods 0.000 description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052979 sodium sulfide Inorganic materials 0.000 description 12
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 carboxylate methyl ester Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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 belongs to waste and old lithium ion battery recycling fields, the battery pack of waste and old lithium ion battery or the battery cell obtained after disassembling are placed in the solution (salting liquid) dissolved with reproducibility salt and discharge by the charging method for specifically disclosing a kind of waste and old lithium ion battery high-efficiency cleaning；The reproducibility salt discharges prior to OH- in aqueous solution.The reproducibility salt is that water soluble sulphurizing salt and/or sulphur hydrogenate salt.The present invention passes through the study found that discharge in salting liquid of the present invention, passes through oxide-reduction method, realizes the electric discharge of waste and old lithium ion battery residual electricity.By the method for the invention, it can be achieved that efficient discharge, not only discharge time is obviously shortened, additionally aids and reach thoroughly electric discharge (being discharged to 0V), be only capable of reaching the charging method of 0.7V compared to existing method, have a clear superiority.
Description
Technical field
The present invention relates to waste and old lithium ion battery recycling field, the high-efficiency cleaning for being related specifically to waste and old lithium ion battery is put
Electricity, in terms of belonging to waste and old lithium ion battery recycling field.
Background technique
With the high speed development of modernization science and technology, social energy and environment ecological pollution problem becomes increasingly conspicuous, various discarded
Battery to environment and ecology pollution problem oneself through the focus at social concerns.And nickle cobalt lithium manganate ion battery is due to capacity
The features such as height, stable cycle performance, high workbench voltage, is widely used in power battery and energy-storage battery, and power and storage
It can the typically larger than conventional compact battery of demand of the battery to battery material.Therefore, in the following 3-5, will have a large amount of useless
Old lithium ion battery is scrapped, and recycling is carried out to it has very high social value.
However, waste and old lithium ion battery still remains substantial portion of voltage, in order to ensure personnel and equipment safety must be into
Row discharge operation makes within the near safe range of residual voltage.It is domestic at present that still individually waste and old lithium ion battery electric discharge is not ground
The recycling focus of the report studied carefully, waste and old lithium ion battery is concentrated mainly on back segment Product recycling, is closed to leading portion discharge treatment
Note degree is less, and the NaCl solution for generalling use 5-10% carries out discharge operation.As 106558739 A of Chinese patent CN is announced
Electric discharge behaviour will be carried out before battery crushing dismantling by referring in " based on lithium ion battery high efficiente callback separating technology in waste mobile phone "
Make, impregnates 48h using 10% NaCl salting liquid and reach the requirement disassembled safely to battery residual voltage.Using 5-10%'s
NaCl salting liquid, which carries out battery discharge operation, can make old and useless battery residual voltage reach the requirement disassembled safely, but discharge rate compared with
Slowly, generally to impregnate above for 24 hours makes the near 1V of residual voltage hereinafter, and can introduce the chloride ion for being difficult to remove and enter leachate
In subsequent impurity and purification and Product recycling stage are affected.What for another example 104538695 A of Chinese patent CN was announced is " useless
The method for recycling metal in nickle cobalt lithium manganate battery and preparing nickle cobalt lithium manganate " utilizes 0.1-1mol/ before battery crushing dismantling
The NaOH solution of L carries out the discharge operation of 1-3h, OH to battery at room temperature-Compare Cl in aqueous solution-It is more difficult to discharge, uses
NaOH solution will certainly reduce the discharge rate and discharge effect of battery, and NaOH can make aluminum hull when handling soft-package battery
The leakage of electrolyte is caused to pollute water quality at corrosion.
To sum up, in existing lithium ion recycling discharge process, also generally existing discharge time is long (it is generally necessary to more than for 24 hours),
And discharge effect is undesirable, is only capable of being discharged to 0.7V or so, and in treatment process, easily corrode battery pack, leads to the electricity of severe toxicity
Solution liquid leaks in electric discharge system, totally unfavorable to personnel and Environmental security.
Summary of the invention
The skills such as discharge time is long, discharge effect is undesirable existing for the charging method for the existing lithium ion battery recycling of solution
Art problem, the present invention provides a kind of charging methods of lithium ion battery high-efficiency cleaning, it is intended to while shortening discharge time,
Improve discharge effect.
A kind of charging method of waste and old lithium ion battery is obtained by the battery pack of waste and old lithium ion battery or through dismantling
Battery cell, which is placed in the solution (present invention is also referred to as salting liquid) dissolved with reproducibility salt, to discharge；
The reproducibility salt discharges prior to OH- in aqueous solution.
The present invention passes through the study found that discharging in salting liquid of the present invention, by oxide-reduction method, in fact
The electric discharge of existing waste and old lithium ion battery residual electricity.By the method for the invention, it can be achieved that efficient discharge, the study found that of the invention
Not only discharge time is obviously shortened method, additionally aids and reaches thoroughly electric discharge (being discharged to 0V), is only capable of reaching compared to existing method
To the discharge effect of 0.7V, have a clear superiority.In addition, the method for the present invention will not corrosion cell group (or battery cell) device,
Personnel and environment will not be caused unfavorable shadow by electrolyte (such as the carboxylate methyl ester class) leakage that will not make severe toxicity in discharge process
It rings, the method for the present invention is truly realized efficiently, cleanly the electric discharge for making waste and old lithium ion battery, is conducive to industrial practical application.
Technical solution of the present invention, the activity of the reproducibility in aqueous solution are necessary prior to OH-.As excellent
Choosing, the reproducibility salt are that water soluble sulphurizing salt and/or sulphur hydrogenate salt.
Further preferably, the water soluble sulphurizing salt is the sulfide of alkali metal；The sulphur hydrogenation salt is alkali gold
The sulfohydrate of category.
Still more preferably, the reproducibility salt be vulcanized sodium, potassium sulfide, NaHS, in potassium bisulfide at least
It is a kind of.
Most preferably, the reproducibility salt is vulcanized sodium.The study found that the effect discharged using the solution of the vulcanized sodium
Fruit is more excellent, and discharge time is shorter, and discharge effect (degree of discharge) can easily reach 0V, has more preferably discharge effect.
Solution of the present invention dissolved with reproducibility salt is preferably the aqueous solution of the reproducibility salt, and described is molten
Allow in liquid system containing some solvents than water, the solvent is preferably and water is infinitely than miscible solvent.
Research also found, control the mass percent in the reproducibility salt of suitable solution, helps further to be promoted and put
Electrical efficiency further improves discharge effect.
Preferably, the concentration of reproducibility salt is not less than 5wt% in the solution dissolved with reproducibility salt.It is preferred at this
Under concentration, it can be discharged to 0V in 14h, technical effect is excellent.
Further preferably, in the solution dissolved with reproducibility salt, the concentration of reproducibility salt is 5~20wt%.
Still more preferably, in the solution dissolved with reproducibility salt, the concentration of reproducibility salt is 10~15wt%.Study table
Bright, under the preferred concentration, the time being discharged under 0V can foreshorten to 6h, and discharge effect is more preferable, and discharging efficiency is more excellent.
The present inventor's research it has also been found that, to the temperature in discharge process, controlling the pH of discharge process, discharge process and
The operation such as conductive material is added in solution dissolved with reproducibility salt, can further improve discharge effect, is shortened discharge time, is changed
Kind discharge effect.
Preferably, the pH of the solution dissolved with reproducibility salt is 7-10.The pH is starting dissolved with reproducibility salt
The pH of solution；Further preferably pH to 7~8.
Further preferably, the pH of the solution system dissolved with reproducibility salt is 7~7.5.
Preferably, the temperature of solution of the control dissolved with reproducibility salt is 25-35 DEG C in discharge process.Described is molten
The temperature that solution has the temperature of the solution of reproducibility salt to that is to say discharge process.
Further preferably, in discharge process, the temperature of solution of the control dissolved with reproducibility salt is 25-30 DEG C.Control exists
Under the preferred discharge temp, discharging efficiency can be further promoted, discharge effect is further improved.
Preferably, also containing conductive material in the solution dissolved with reproducibility salt.By in discharge process
Conductive material is added in solution dissolved with reproducibility salt, can further improve discharge effect, promotes discharging efficiency.
Preferably, the conductive material is at least one of graphite, graphite oxide, electrically conductive polyaniline.
Preferably, the volume fraction of the conductive material is 5- in the solution dissolved with reproducibility salt
20%.
Preferably, the waste and old lithium ion battery is waste and old ternary power battery, cobalt acid lithium battery, LiMn2O4 electricity
Pond, one or more of ferric phosphate lithium cell.
Preferably, the battery pack, battery cell residual voltage be not less than 1V, preferably 3.8V~3.85V.
Preferably, time of the voltage lower than 1V after electric discharge is not higher than 14h.Discharge time of the invention is significantly lower than
Existing method, even so, moreover it is possible to guarantee more preferably discharge effect.
A kind of charging method of preferred new waste and old lithium ion battery high-efficiency cleaning of the present invention, key step are as follows:
Step 1: waste and old power battery pack is disassembled into waste and old lithium ion battery monomer；
Step 2: survey press operation being carried out to the waste and old lithium ion battery monomer that step 1 obtains, can be used existing equipment fast
Speed continuously separates the battery cell to discharge, obtains the battery cell for needing to carry out discharge treatment；
Step 3: the battery cell for needing to carry out discharge treatment that step 2 is obtained is launched to the appearance equipped with various salts
Discharge operation is carried out in device, adjusts the physical parameter of solution and adds solid conduction powder enhanced discharge effect；
Step 4: record detects the residual voltage of battery in corresponding solution under different time points until 1V is hereinafter, comparison is different
Time needed for being discharged to safe current potential under salting liquid and discharge effect.
Waste and old power battery pack described in step 1 is preferably waste and old ternary power battery pack.
The battery cell that the battery cell to discharge is preferably higher than 1V to residual voltage is carried out described in step 2.
Salting liquid described in step 3 is vulcanized sodium, one or more of sodium hydrosulfide；The solution physics ginseng
Number refers to the temperature of solution, pH value, one or more of concentration；The solid powder is graphite, and graphite oxide is conductive poly-
One or more of aniline.
Concentration of salt solution described in step 3 is 5-20%, and temperature is 25-35 DEG C, and pH value is 7 or so；Institute's reinforcing body powder
The mass fraction at end is 5-20%.
The object of the present invention is to provide a kind of charging methods of new waste and old lithium ion battery high-efficiency cleaning.Using simple
Electrolysis principle anode release electronic cathode obtains electronics, and the solution using the reproducibility salt for being easy to hydroxyl electric discharge is situated between as electric discharge
Matter substitutes the NaCl solution for the 5-10% that current main-stream uses, and avoids the introducing of chloride ion while can realize applying waste lithium ionic electricity
The high-efficiency cleaning in pond discharges.
The utility model has the advantages that
1) progress discharge operation avoids and handles bring security risk to subsequent recovery before waste and old lithium ion battery dismantling,
Detection monitoring fast and safely can be carried out to waste and old lithium ion battery residual voltage using existing equipment, realize that discharge operation connects
It is continuous to carry out without security risk；
2) it has been put forward for the first time and has added conductive powder mixing to realize that solid-liquid discharges jointly using sodium sulfide solution and sodium sulfide solution
Technology avoids the use of mainstream discharge medium NaCl salting liquid to which no chloride ion introduces and avoids pernicious gas chlorine
It generates, subsequent production is not had an impact, it can be achieved that waste and old lithium ion battery high-efficiency and continuous cleaner discharge.
3) conductive powder solid-liquid collaboration discharge technology is added to discharge in old and useless battery using sodium sulfide solution or sodium sulfide solution
It is harmless to battery case in the process, it avoids using other discharge mediums such as sodium hydroxide, sodium chloride solution is to battery case
Corrosion cause electrolyte leakage pollute water quality.
4) this method suitably forms continuous operation, will not generate secondary pollution take into account environment benefits and economic gains, simple process,
Production cost is low, is suitble to large-scale industrial production.
5) the method for the present invention is used, the technology drawback that existing method can not thoroughly discharge is overcome, it is residual after discharge treatment
Stay voltage that can be down to 0V；
6) present invention is obviously shortened discharge time, and the time for being discharged to 0V can foreshorten to 6h.
Detailed description of the invention
Fig. 1 is the battery discharge effect picture using the sodium sulfide solution of various concentration.
Fig. 2 is the battery discharge effect picture using the sodium sulfite solution of various concentration.
Case is embodied
The following are exemplary embodiments of the invention, and however, it is to be understood that the present invention is not limited to these embodiments.
Following percentage refers both to mass percent unless specified or limited otherwise.
Following embodiment and comparative example, the waste and old power battery are waste and old 523 type ternary lithium battery.
Embodiment 1
Waste and old power battery pack is disassembled into battery cell using automation device for disassembling, is then proceeded to using existing useless
Used batteries residual voltage detection device carries out the battery that residual voltage detection separating residual voltage is higher than 1V to each battery cell
Monomer enters electric discharge process.5 groups of residual voltages are taken to be immersed in the battery cell of 3.8V~3.85V equipped with 5%Na2S solution
In open-top receptacle, the pH value of solution is adjusted to 7~7.5, temperature is 25 DEG C, measures the residual voltage of 5 groups of battery every 1h
And it records until electric discharge is complete.At this point, old and useless battery near 0V of residual voltage after impregnating 14h.
Embodiment 2
Waste and old power battery pack is disassembled into battery cell using automation device for disassembling, is then proceeded to using existing useless
Used batteries residual voltage detection device carries out the battery that residual voltage detection separating residual voltage is higher than 1V to each battery cell
Monomer enters electric discharge process.Battery cell of 5 groups of residual voltages in 3.8V~3.85V is taken to be immersed in equipped with 5%Na2S solution
In open-top receptacle, the pH value of solution is adjusted to 7~7.5, temperature is 30 DEG C, measures the residual voltage of 5 groups of battery every 1h
And it records until electric discharge is complete.At this point, old and useless battery near 0V of residual voltage after impregnating 12h.
Embodiment 3
Waste and old power battery pack is disassembled into battery cell using automation device for disassembling, is then proceeded to using existing useless
Used batteries residual voltage detection device carries out the battery that residual voltage detection separating residual voltage is higher than 1V to each battery cell
Monomer enters electric discharge process.5 groups of residual voltages are taken to be immersed in the battery cell of 3.8V~3.85V equipped with 10%Na2S solution
In open-top receptacle, the pH value of solution is adjusted to 7~7.5, temperature is 30 DEG C, measures the residual voltage of 5 groups of battery every 1h
And it records until electric discharge is complete.At this point, old and useless battery near 0V of residual voltage after impregnating 6h.
Embodiment 4
Waste and old power battery pack is disassembled into battery cell using automation device for disassembling, is then proceeded to using existing useless
Used batteries residual voltage detection device carries out the battery that residual voltage detection separating residual voltage is higher than 1V to each battery cell
Monomer enters electric discharge process.5 groups of residual voltages are taken to be immersed in the battery cell of 3.8V~3.85V equipped with 10%Na2S solution
In open-top receptacle, the pH value of solution is adjusted to 7~7.5, temperature is 30 DEG C, and the electrically conductive polyaniline powder of 10 (volume) % is then added
End stirring measures the residual voltage of 5 groups of battery and record until electric discharge is complete to being uniformly mixed, every 1h.At this point, waste and old
Battery near 0V of residual voltage after impregnating 4.5h.Putting for old and useless battery can be further speeded up using the form of solid-liquid joint electric discharge
Electrical efficiency.
Comparative example 1
This comparative example is inquired into, using Na2SO3The replacement Na2S, specific as follows:
Waste and old power battery pack is disassembled into battery cell using automation device for disassembling, is then proceeded to using existing useless
Used batteries residual voltage detection device carries out the battery that residual voltage detection separating residual voltage is higher than 1V to each battery cell
Monomer enters electric discharge process.Battery cell of 5 groups of residual voltages in 3.8V~3.85V is taken to be immersed in equipped with 5%Na2SO3 solution
Open-top receptacle in, adjust the pH value of solution to 7~7.5, temperature is 25 DEG C, measures the residual electricity of 5 groups of batteries every 1h
It presses and records until electric discharge is complete.At this point, old and useless battery residual voltage after impregnating for 24 hours is 1.4V.
Comparative example 2
This comparative example is inquired into, using Na2SO3The replacement Na2S, and discharge at 30 DEG C, it is specific as follows:
Waste and old power battery pack is disassembled into battery cell using automation device for disassembling, is then proceeded to using existing useless
Used batteries residual voltage detection device carries out the battery that residual voltage detection separating residual voltage is higher than 1V to each battery cell
Monomer enters electric discharge process.Battery cell of 5 groups of residual voltages in 3.8V~3.85V is taken to be immersed in equipped with 5%Na2SO3 solution
Open-top receptacle in, adjust the pH value of solution to 7~7.5, temperature is 30 DEG C, measures the residual electricity of 5 groups of batteries every 1h
It presses and records until electric discharge is complete.At this point, old and useless battery residual voltage after impregnating for 24 hours is 1.25V.
Comparative example 3
This comparative example is inquired into, using Na2SO3The replacement Na2S, and discharge under 10% concentration, it is specific as follows:
Waste and old power battery pack is disassembled into battery cell using automation device for disassembling, is then proceeded to using existing useless
Used batteries residual voltage detection device carries out the battery that residual voltage detection separating residual voltage is higher than 1V to each battery cell
Monomer enters electric discharge process.Battery cell of 5 groups of residual voltages in 3.8V~3.85V is taken to be immersed in equipped with 10%Na2SO3 solution
Open-top receptacle in, adjust the pH value of solution to 7~7.5, temperature is 30 DEG C, measures the residual electricity of 5 groups of batteries every 1h
It presses and records 7 until electric discharge is complete.At this point, old and useless battery residual voltage after impregnating for 24 hours is 1.1V.
Comparative example 4
This comparative example is inquired into, and is discharged using conventional NaCl, specific as follows:
Waste and old power battery pack is disassembled into battery cell using automation device for disassembling, is then proceeded to using existing useless
Used batteries residual voltage detection device carries out the battery that residual voltage detection separating residual voltage is higher than 1V to each battery cell
Monomer enters electric discharge process.Battery cell of 5 groups of residual voltages in 3.8V~3.85V is taken to be immersed in equipped with 5%NaCl solution
In open-top receptacle, the pH value of solution is adjusted to 7~7.5, temperature is 30 DEG C, measures the residual voltage of 5 groups of battery every 1h
And it records until electric discharge is complete.At this point, old and useless battery residual voltage after impregnating for 24 hours is 0.7V.
Comparative example 5
Blank control:
Waste and old power battery pack is disassembled into battery cell using automation device for disassembling, is then proceeded to using existing useless
Used batteries residual voltage detection device carries out the battery that residual voltage detection separating residual voltage is higher than 1V to each battery cell
Monomer enters electric discharge process.Battery cell of 5 groups of residual voltages in 3.8V~3.85V is taken to be immersed in the open-top receptacle equipped with pure water
In, the pH value of solution is adjusted to 7~7.5, and temperature is 30 DEG C, measures the residual voltage of 5 groups of battery every 1h and records straight
It is complete to electric discharge.At this point, old and useless battery residual voltage after impregnating for 24 hours is thrown away as 3.8 ± 0.3V.
Claims (10)
1. a kind of charging method of waste and old lithium ion battery, which is characterized in that by the battery pack or warp of waste and old lithium ion battery
It disassembles obtained battery cell and is placed in the molten discharge in liquid dissolved with reproducibility salt；
The reproducibility salt discharges prior to OH- in aqueous solution.
2. the charging method of waste and old lithium ion battery as described in claim 1, which is characterized in that the reproducibility salt is can
Water-soluble sulphurizing salt and/or sulphur hydrogenate salt.
3. the charging method of waste and old lithium ion battery as claimed in claim 2, which is characterized in that the reproducibility salt is sulphur
Change at least one of sodium, potassium sulfide, NaHS, potassium bisulfide.
4. the charging method of waste and old lithium ion battery as claimed in any one of claims 1 to 3, which is characterized in that dissolved with also
In the solution of originality salt, the concentration of reproducibility salt is not less than 5wt%；Preferably 5~20wt%.
5. the charging method of waste and old lithium ion battery as described in claim 1, which is characterized in that dissolved with the molten of reproducibility salt
The pH of liquid is 7-10.
6. the charging method of waste and old lithium ion battery as described in claim 1, which is characterized in that in discharge process, control molten
The temperature that solution has the solution of reproducibility salt is 25-35 DEG C.
7. the charging method of waste and old lithium ion battery as described in claim 1, which is characterized in that in discharge process, control molten
The temperature that solution has the solution of reproducibility salt is 25-30 DEG C.
8. the charging method of waste and old lithium ion battery as described in claim 1, which is characterized in that described is dissolved with reproducibility
In the solution of salt, also contain conductive material, the conductive material is graphite, in graphite oxide, electrically conductive polyaniline, polypyrrole
It is at least one；The volume fraction of preferred conductive material is 5-20%.
9. the charging method of waste and old lithium ion battery as described in claim 1, which is characterized in that the applying waste lithium ionic electricity
Pond is waste and old ternary power battery, cobalt acid lithium battery, lithium manganate battery, one or more of ferric phosphate lithium cell；
Preferably, the battery pack, battery cell residual voltage be not less than 1V, preferably 3.8V~3.85V.
10. the charging method of waste and old lithium ion battery as described in claim 1, which is characterized in that the voltage after electric discharge is lower than
The time of 1V is not higher than 14h.
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| CN113809426A (en) * | 2021-09-17 | 2021-12-17 | 格林美股份有限公司 | Discharging method of waste lithium ion battery |
| CN114094216A (en) * | 2021-10-29 | 2022-02-25 | 格林美股份有限公司 | Efficient discharge method for waste lithium ion battery module |
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| SE2250287A1 (en) * | 2022-03-03 | 2023-09-04 | Northvolt Revolt Ab | Enhanced discharge processes |
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