CN1547283A - A novel method used for non destructive battery regeneration - Google Patents
A novel method used for non destructive battery regeneration Download PDFInfo
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- CN1547283A CN1547283A CNA2003101172609A CN200310117260A CN1547283A CN 1547283 A CN1547283 A CN 1547283A CN A2003101172609 A CNA2003101172609 A CN A2003101172609A CN 200310117260 A CN200310117260 A CN 200310117260A CN 1547283 A CN1547283 A CN 1547283A
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- regeneration
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- 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
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Abstract
The invention researches the failure reason pointing to the battery, which researches the feasibility of performance restoration such as the capacity, circular lifespan, discovers the new path for regenerating the non-destructive battery, proposes an efficient method-supersonic wave processing method, it uses the special 'cavitation effect', it can achieves the aim of regeneration, thus it realizes the circular regeneration of the battery, the effect is prominent and easy. The invention can reduce the cost of the secondary battery such as nickel-hydrogen and nickel-cadmium.
Description
Technical field
The invention belongs to the recovery and the cycling and reutilization technical field of secondary cell.
Background technology
Since the eighties in 20th century, emergence along with information industry, portable electronic such as mobile communication, notebook computer equipment develops rapidly, have the energy density height, metal hydride-nickel (MH-Ni) battery pollution-free, good characteristic such as electric current fast charging and discharging greatly is used widely, occupied battery industry than the big market share.Along with going deep into of research work and constantly bringing forth new ideas of technology, the MH-Ni battery has obtained the generally attention of countries in the world and support energetically in the application that electric tool, motor vehicle (EV), engine and storage battery mix hybrid electric vehicles aspects such as (HEV) of using, and becomes the important representative of novel energy after traditional energies such as coal, oil.Particularly the populous and living standards of the people of China improves constantly, the MH-Ni battery will be widely used and develop, and simultaneously its environment and resource problem of bringing will day by day highlight, and the recycling of old and useless battery becomes people at present than one of question of common concern.
It has been generally acknowledged that because the basic composition of the structure of MH-Ni battery and positive electrode is close with the Ni/Cd battery, handles waste and old Ni/Cd battery at present and mainly contain pyrometallurgy and hydrometallurgy, they also can be used for handling waste and old MH-Ni battery in principle.But compare with the negative material (CdO) that composition is more single in the Ni/Cd battery, because the metal hydride alloy electrode material of MH-Ni battery contains multiple alloying element (as Ni, Co, La, Ce, Mn, Fe, Zr, Ti etc.) usually, therefore the particularity that is had according to the MH-Ni battery, and consider the technical feasibility and the economy of old and useless battery material regeneration metallurgical process, now proposed to reclaim the processing method of waste and old MH-Ni battery material at different recovery targets, different negative materials etc.
It is simple, to the hydrogen-storage alloy type handled without limits and can partly utilize the existing advantages such as production equipment of handling waste and old Ni/Cd battery that the pyrometallurgy flow process has processing procedure, but it is lower to reclaim the alloy economic worth of gained.According to the literature, several companies such as Ri Ben Sumitomo Metal Industries, three moral metals have adopted this method that discarded MH-Ni battery is handled.Pyrogenic process specific to nickel reclaims, it is the electric furnace smelting that adopts higher temperature, but the product that pyrogenic process reclaims is the Fe-Ni alloy, and the separation of the nickel of being unrealized is reclaimed, because the many forms with hydroxide of nickel exist in the battery, can become oxide during heating, so when adopting pyrogenic process to reclaim, need to add carbon dust and make reducing agent.Pingwei Zhang (Hydrometallurgy, 1998, (50): 61-75) wait the people to utilize valuable metal in the hydrometallurgic recovery waste nickel hydrogen battery, proposed the recovery battery waste and mainly contained 5 unit operations steps and form, and the optimum condition that draws leaching is: 3mol/LHCl, 95 ℃, solid-to-liquid ratio is 1: 9, processing time 9h, with this understanding, can leach＞96% nickel 99% rare earth and 100% cobalt.(US 5858061,1999-01-12) wait the people to use H earlier for Klaus Kleinsorgen
2SO
4Dissolving Ni-MH battery waste material, then digestion liquid is carried out solvent extraction, select and the two-phase volume ratio by control pH value, solvent, rare earth element, iron, aluminium etc. will be separated out with the form of precipitation, then there are nickel and the cobalt identical in the liquid phase with ratio in the waste material, by with one-step electrolysis the intermediate product of handling being made the intermediate alloy that can utilize again, rare earth element last and that be settled out is reprocessed into mishmetal through electric power metallurgy and is used for making new hydrogen bearing alloy then.
Up to now, though both at home and abroad the recovery and the regeneration techniques of waste and old MH-Ni battery launched a series of research work, and obtained certain progress, but still have following technical bottleneck: (1) existing battery recovery technology is still immature, also only is to rest on traditional pyrogenic process or the hydrometallurgic recovery technology; (2) recovery rate of valuable metals and economic worth are all lower, the cost consumption height; (3) present Retrieving Technology of Waste and Used Battery is complicated and use various chemical reagent, and this certainly will can cause secondary pollution to surrounding enviroment again.
The present invention is primarily aimed at the various failure causes of MH-Ni battery, studies the feasibility of its capacity restoration, has explored nondestructive physics of multiple battery or chemical regeneration method.The present invention by adopting the method for ultrasonic oscillation, utilizes its distinctive " cavitation effect " first, makes battery can reach the purpose of battery capacity regeneration under nondestructive condition, thereby has realized the cycling and reutilization of MH-Ni battery to a certain extent.And finding one of best processing method ultrasonic Treatment, this method is simple, effect is obvious, and can not cause any secondary pollution to environment.
Summary of the invention
The present invention is achieved in that the method that adopts ultrasonic oscillation, utilizes its distinctive " cavitation effect ", makes battery can reach the purpose of battery capacity regeneration under nondestructive condition, thereby has realized the cycling and reutilization of battery to a certain extent.And control ultrasonic wave action time, temperature, ultrasonic wave interaction medium.Action time (more than 0.1 second), operative temperature (more than 50 degree), ultrasonic medium (organic or inorganic solution such as water, alkali lye, gasoline) etc.The present invention is primarily aimed at the cycling and reutilization of MH-Ni battery.
Make 200 all charge and discharge circulation lifes and consistency Ni-MH battery preferably with 4 groups, be used for ultrasonic Treatment battery recycling experiment of the present invention.A, B, C, D four Battery packs are chosen certain ultrasonic wave time, ultrasonic wave medium, temperature constant (placing insulating box) respectively.Ultrasonic Treatment is carried out the check and analysis of chemical property and positive and negative electrode material aspect thereof after finishing to battery.
Through the Electrochemical Detection excellent performance, method of testing is through the battery after the said method regeneration: the 1C 60min that charges, shelve 30min, and 1C is discharged to 1V; 0.5C charging 140min shelves 30min, 0.5C is discharged to 1V, be circulated to capacity attenuation and be former capacity 80% till.This battery and positive and negative pole material The performance test results such as Fig. 1, Fig. 2 and shown in Figure 3.
Description of drawings
The chemical property of Fig. 1-battery behind different ultrasonic wave time effects relatively
Fig. 2-positive and negative electrode is through the X-ray diffractogram of different ultrasonic wave after the time
Fig. 3-continuation charge and discharge circulation life the curve of battery after the ultrasonic wave effect
Fig. 1 for the battery after the method provided by the invention regeneration with without the discharge capacity comparison diagram of battery under different discharging currents of regenerating.In Fig. 1, After represents with the battery capacity test curve after the method regeneration provided by the invention, Before represents the battery capacity test curve without regeneration, as seen from the figure, regenerated the discharge capacity of battery apparently higher than the discharge capacity of battery of regeneration not with method provided by the invention.
Fig. 2 is battery after regenerating with method provided by the invention and the battery X-ray diffractogram of not regenerating.In Fig. 2, After represents with the battery X-ray diffractogram after the method regeneration provided by the invention, Before represents the battery X-ray diffractogram without regeneration, as seen from the figure, the inertia rare earth oxide that the battery of regenerating with method provided by the invention can make its negative terminal surface segregation go out comes off, and exposes fresh active surface again, has increased participation reactive activity center, improve the electro catalytic activity of electrode, battery capacity is increased.
Fig. 3 is for continuing 0.5C charge and discharge circulation life curve with the battery after the method regeneration provided by the invention.As seen from the figure, the battery of regenerating with method provided by the invention can be proceeded to circulate more than 100 weeks again.
The battery non-destructive novel process for regenerating that is used for provided by the invention owing to the tangible dispersion phenomenon of electrode material activity material, can increase and participate in the reactive activity center, is improved the electro catalytic activity of electrode, thereby is caused the increase of capacity.And its surface after ultrasonic Treatment, negative alloy powder surface is smooth further, be tangible metallic luster, and the EDAX quantitative analysis of mating surface element, show that the inertia rare earth oxide that ultrasonic wave may make the negative terminal surface segregation go out comes off, and expose fresh active surface again, improve the electro catalytic activity of electrode, its capacity is increased.Battery performance and cycle life after the method that adopts the technology of the present invention to provide is regenerated are improved, and have improved 13.30% as AA type battery 0.5C discharge capacity; The 1C discharge capacity has improved 10%; Cycle life has increased by 103 weeks.The raising of these performances can promote the development of secondary cell cost degradations such as ni-mh, NI-G.Secondary cell regeneration techniques provided by the invention compared with prior art, method is easy, easy operating.
Embodiment
Be example with AA type Ni-MH battery below:
Embodiment 1:
To make 200 all charge and discharge circulation lifes and consistency AA type Ni-MH battery preferably, and be used for ultrasonic Treatment battery recycling experiment of the present invention, the ultrasonic wave medium is a water, and the ultrasonic wave time is 2 hours, and temperature constant is 55 degree (placing insulating box).Ultrasonic Treatment makes battery 0.5C discharge capacity improve 6.3% after finishing, and the 1C discharge capacity has improved 5%.
Embodiment 2:
To make 200 all charge and discharge circulation lifes and consistency AA type Ni-MH battery preferably, and be used for ultrasonic Treatment battery recycling experiment of the present invention, the ultrasonic wave medium is a water, and the ultrasonic wave time is 4 hours, and temperature constant is 40 degree (placing insulating box).Ultrasonic Treatment makes battery 0.5C discharge capacity improve 8.25% after finishing, and the 1C discharge capacity has improved 7.3%.
Embodiment 3:
To make 200 all charge and discharge circulation lifes and consistency AA type Ni-MH battery preferably, be used for ultrasonic Treatment battery recycling of the present invention experiment, the ultrasonic wave medium be alkali lye+, the ultrasonic wave time is 6 hours, temperature constant is 55 degree (placing insulating box).Ultrasonic Treatment makes battery 0.5C discharge capacity improve 14.2% after finishing, and the 1C discharge capacity has improved 16.6%.
Embodiment 4:
To make 200 all charge and discharge circulation lifes and consistency AA type Ni-MH battery preferably, and be used for ultrasonic Treatment battery recycling experiment of the present invention, the ultrasonic wave medium is a water, and the ultrasonic wave time is 8 hours, and temperature constant is 40 degree (placing insulating box).Ultrasonic Treatment makes battery 0.5C discharge capacity improve 2.4% after finishing, and the 1C discharge capacity has improved 3.9%.
Claims (5)
1. one kind is used for battery non-destructive novel process for regenerating, it is characterized in that: the ultrasonic oscillation method of employing, utilize its distinctive " cavitation effect ", and make quality rebuildings such as secondary battery capacity.And control ultrasonic wave action time, temperature, ultrasonic wave interaction medium.
2. a kind of battery non-destructive novel process for regenerating that is used for according to claim 1, it is characterized in that: secondary cell is mainly ni-mh, nickel-cadmium cell;
3. a kind of battery non-destructive novel process for regenerating that is used for according to claim 1, it is characterized in that: the ultrasonic wave that is adopted is action time: more than 0.1 second;
4. a kind of battery non-destructive novel process for regenerating that is used for according to claim 1, it is characterized in that: the ultrasonic wave operative temperature that is adopted is: more than-50 degree;
5. a kind of battery non-destructive novel process for regenerating that is used for according to claim 1, it is characterized in that: the ultrasonic wave interaction medium that is adopted is: organic or inorganic solution such as water, alkali lye, gasoline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101172609A CN1248354C (en) | 2003-12-10 | 2003-12-10 | A novel method used for non destructive battery regeneration |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101172609A CN1248354C (en) | 2003-12-10 | 2003-12-10 | A novel method used for non destructive battery regeneration |
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| CN1547283A true CN1547283A (en) | 2004-11-17 |
| CN1248354C CN1248354C (en) | 2006-03-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2003101172609A Expired - Fee Related CN1248354C (en) | 2003-12-10 | 2003-12-10 | A novel method used for non destructive battery regeneration |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109923729A (en) * | 2017-07-27 | 2019-06-21 | 株式会社Lg化学 | The method of redgenerated cell |
| CN110178262A (en) * | 2017-10-24 | 2019-08-27 | 株式会社Lg化学 | The method of redgenerated cell unit |
| CN111684089A (en) * | 2017-11-28 | 2020-09-18 | 尼拉国际股份公司 | Grinding of recovered negative electrode material |
-
2003
- 2003-12-10 CN CNB2003101172609A patent/CN1248354C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109923729A (en) * | 2017-07-27 | 2019-06-21 | 株式会社Lg化学 | The method of redgenerated cell |
| US11387499B2 (en) | 2017-07-27 | 2022-07-12 | Lg Energy Solution, Ltd. | Method for regenerating cell |
| CN110178262A (en) * | 2017-10-24 | 2019-08-27 | 株式会社Lg化学 | The method of redgenerated cell unit |
| CN110178262B (en) * | 2017-10-24 | 2022-05-24 | 株式会社Lg化学 | Method for regenerating battery cell |
| CN111684089A (en) * | 2017-11-28 | 2020-09-18 | 尼拉国际股份公司 | Grinding of recovered negative electrode material |
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| Publication number | Publication date |
|---|---|
| CN1248354C (en) | 2006-03-29 |
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