CN101183740A - Method of controlling fragmentation and recovery of waste battery and system thereof - Google Patents

Method of controlling fragmentation and recovery of waste battery and system thereof Download PDF

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Publication number
CN101183740A
CN101183740A CNA2007101254895A CN200710125489A CN101183740A CN 101183740 A CN101183740 A CN 101183740A CN A2007101254895 A CNA2007101254895 A CN A2007101254895A CN 200710125489 A CN200710125489 A CN 200710125489A CN 101183740 A CN101183740 A CN 101183740A
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battery
waste battery
control
powder
collection
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CN100514745C (en
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许开华
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GEM Co Ltd China
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Shenzhen Gem High Tech Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Abstract

The invention relates to a controllably-crushing recovery method and system of scrap batteries, comprising the following steps that: the scrap batteries are separated and classified to obtain a collection of lithium-ion batteries; the casings of the lithium-ion batteries are shelled by a scrap-battery rejuvenator to obtain a collection of lithium-ion battery content; the collected lithium-ion battery content is physically separated to obtain a collection of aluminium positive plates and positive active coatings on the positive plates; the aluminium positive plates and the positive active coatings on the positive plates are sent into a controllably-crushing device of scrap batteries and processed controllably-crushing to obtain a collection of mixture of aluminium granule and positive powder; the mixture of aluminium granule and positive powder is subtly sieved and separated to respectively obtain the aluminium granule and the positive powder. The invention has the advantages of greatly reducing environmental pollution of recovery process, less material-separating energy consumption, being close to 90% of intrinsic purity for the lithium cobalt oxide powder from recovery and facilitating economic running.

Description

Broken recovery method of a kind of control of waste battery and system thereof
Technical field
The present invention relates to a kind of environmental protection and reclaimer, more particularly, the present invention relates to a kind of recovery production technology and equipment that contains the aluminium waste battery.
Background technology
Lithium rechargeable battery, since nineteen ninety realizes commercially producing application, because have that volume is little, in light weight, storage electric energy power is big, charging rate fast, the serviceability temperature wide ranges, the operating time is long and longly recycle plurality of advantages such as life-span, thereby is widely used in video camera, mobile phone, notebook computer and Portable Measurement Instrument etc.
Lithium rechargeable battery, comprise the shell of metal or plastics and the electric core of content, the electricity core comprises positive pole, negative pole, barrier film, generally, positive electrode active materials is made up of about 90% cobalt acid lithium powder, the agent of 7-8% carbon black conductive, 3-4% organic bond, and positive electrode active materials is coated on the aluminium flake collector body; Negative active core-shell material is made up of about 94% carbon element powder, 5-6% organic bond, and negative active core-shell material is coated on the copper sheet collector body.Lithium ion battery can be because electrode expands, capacity descends and scraps through after the discharging and recharging of certain number of times; Also having wide variety of materials in process of production scraps.
Along with technology and expanding economy, the use amount of lithium ion battery constantly increases year by year, and the lithium ion battery of scrapping also will increase considerably year by year.With common mobile phone lithium ion battery is example, and wherein cobalt content is about 15%, and lithium content is about 0.1%, and cobalt is a heavy metal element, can cause bigger harm to environment.Waste and old lithium ion battery or production waste are reclaimed, not only can eliminate the pollution of harmful substance, but also can make full use of resource, thereby have important Significance for Environment and potential economic worth environment.Now, along with the environmental consciousness of entire society is strengthened gradually, and natural resources is in short supply day by day, recycles resource material in the discarded lithium rechargeable battery, reduces waste battery has caused industry day by day to the pollution of environment concern.
After with the lithium rechargeable battery broken shell, the barrier film of metal wherein, plastic casing and content is easy to adopt physical separation method such as gravity, wind-force, magnetic force to be separated and reclaims or handle; And in anode and cathode active materials wherein and aluminium flake, the copper sheet collector body: physical property such as the proportion of copper sheet collector body, mechanical tenacity and even commercial exploitation be worth with its on carbon element powder, organic bond difference bigger, thereby relatively easy separating treatment; In contrast to this, the difference of the proportion of aluminium flake collector body and even commercial exploitation value and the acid of the positive electrode active materials cobalt on it lithium powder is all less, along with the resource growing tension, positive electrode has the more and more higher market price and value, therefore, the requirement that the separation of positive electrode is reclaimed is higher relatively.
In this regard, have application number be 200510018601.6 Chinese patent application file disclose a kind of from waste and old lithium ion battery the method for separating and recovering cobalt, it is characterized in that: after waste and old cobalt acid lithium battery discharge, carry out physics and disassemble, obtain containing the positive electrode of cobalt acid lithium, this positive electrode is calcined or after organic solvent soaks, is peeled off the aluminium flake on the positive electrode, obtain containing the black solid material of cobalt acid lithium, the black solid material that will contain cobalt acid lithium places under the acid condition uses H 2O 2Or Na 2S 2O 3As reducing agent, heating for dissolving obtains containing Co 2+And Li +Solution, be precipitation reagent with NaOH solution again, with the Co in the solution 2+Ion changes into Co (OH) 2Precipitation leaves standstill the back and filters.It is said that this method is simple, convenient, energy-conservation, environment is not impacted; And the purity of this method cobalt and the rate of recovery are all higher.
Also having application number is that 200580020560.2 Chinese patent application file discloses a kind of method of disposing of lithium battery in this processing method, will have that the sheet that is arranged on the positive electrode active materials on the positive electrode collector is anodal to immerse in the oxalic acid solution.Because this oxalic acid treatment can be dissolved to all elemental lithiums that comprise in the positive electrode active materials in the oxalic acid solution, utilize the oxygen that generates by the reaction between positive electrode active materials and the oxalic acid, can make attachment such as positive electrode active materials from the positive electrode collector self-separation.Transition metal contained in the positive electrode active materials changes into insoluble transistion metal compound (oxalates, oxide etc.) by oxalic acid treatment.It is said, just can easily separate with insoluble transition metal as filtering dissolving the elemental lithium that through straightforward procedure.
Above-mentioned processing method adopts dry method or wet method that cobalt acid lithium is separated with aluminium flake, the separation process power consumption is big or still can cause certain pollution to environment, and dry method, wet method expend and more all 90% cobalt acid lithium powder can only be purified several percentage points, be difficult to guarantee economical operation.
Summary of the invention
Above-mentioned shortcoming at prior art, the objective of the invention is to provide a kind of broken recovery method of control and device systems thereof of waste battery, this technology and device systems have following advantage: the environmental pollution of removal process significantly reduces, material separates less energy intensive, reclaims approaching original 90% purity of cobalt acid lithium powder that obtains, and is convenient to economical operation.
For this reason, one of technical solution of the present invention is the broken recovery method of a kind of control of waste battery, and this recovery method comprises the steps: A) waste battery is carried out sorting and grouping, collect and obtain discarded lithium ion battery; B) utilize the waste battery rejuvenator that the shell of lithium ion battery is carried out broken shell, collects and obtain the content of lithium ion battery, and metal or plastic casing are dealt with in addition; C) the lithium ion battery content that collection obtained is through physical separation, collect to obtain aluminium matter positive plate and adhere to anodal active coating on it, and the copper negative plate and the negative electrode active coating of adhering on it deals with in addition; D) the aluminium matter positive plate that collection is obtained and adhere to anodal active coating on it and send into the control breaker of waste battery and control fragmentation is collected the mixture that obtains aluminium matter particle and anodal powder; E) the aluminium matter particle that collection is obtained and the mixture of anodal powder carry out the meticulous sorting of sieving, and aluminium matter particle that obtains respectively and anodal powder carry out the purification of the commercial distribution or the degree of depth then respectively or handle reuse.
Technology of the present invention, adopting a series of physical principles is main process, at tool commercial value in the lithium ion battery with pollute the positive electrode active materials of character, carry out separating treatment, wherein, utilize the aluminium flake collector body on mechanical tenacity with big these characteristics of difference of positive electrode active materials cobalt acid lithium powder, adopted characteristic physics crushing mechanism: multi-disc rectangle frame posture rotatable lamella is being installed on the main shaft, is fixing a plurality of export-oriented cutter pieces, the spacing that the inwall of the outer rim of cutter piece and described tubular framework keeps suitably, fixes crossing on the bridging beam of this rotating frame; Served as bridging beam and on a plurality of export-oriented cutter piece high speed rotating the time, aluminium flake in screen cloth and tubular framework and positive electrode active materials will be under centrifugal actions, move in the space between export-oriented cutter piece and the tubular frame inner wall, because having bigger toughness, aluminium flake is easy to tear, and anodal reactive powder is torn to disintegrate easily in the process at aluminium flake and is recovered to become thinner powder, so, shearing force at high speed rotating, friction, impulsive force, under the synergy of wind-force etc., positive electrode just is fractured into and is the bigger mixture of powders of granularity difference, from the eyelet of parcel screen cloth, fall together, together be collected as screenings.Though this screenings is the mixed-powder thing,, through experiment confirm, the granularity difference of this mixed-powder thing more is adapted to do further meticulous particle size separation completely.And, experiment confirm: separate aluminium flake particle, the positive electrode active material powder that obtains through apparatus of the present invention and system thereof, finally can reaching sieve respectively, to go up aluminium content be that the ratio of 88-90%, positive electrode active material powder is 10-12%, and aluminium content is 0.1-1.0% under the sieve, and the sieve ratio of positive electrode active material powder down is 99.0-99.9%.
Test confirms: separated obtaining cobalt acid lithium powder very near its 90% original purity by this process, can directly sell battery producer, perhaps do very a spot of processing and recover to become purer positive electrode active material powder row utilization or sale again as the commercial distribution product.The purity of aluminium flake particle is also higher, can carry out commercial distribution, also can carry out the difficulty small depth and purify.That is: technology separation process less energy intensive of the present invention, removal process are separated and are not adopted the soda acid chemicals, thereby can significantly reduce environmental pollution, reclaim product and realize economic benefit easily, are convenient to economical operation.
Technology of the present invention also comprises following concrete improvement:
Described steps A) in, described sorting and grouping be adopt gravity, magnetic force, shape difference, actinoscopy X equipment wherein one or more combination come dissimilar waste battery mixtures are carried out.
At described step B) in, described waste battery rejuvenator comprises the drive rod that is located at the protruding sword of battery shaft in nib, advances battery to move in axial nib.
At described step C) in, described physical separation adopts gravity, magnetic force, wherein one or more combination of wind sorting equipment.
Described step C) in, with the copper negative plate that obtains and on the carbonaceous negative electrode active coating of adhering to, carry out wash-out and separate, then, the carbonaceous siccative sent reclaims heat energy in the stove, copper negative plate directly carries out commercial distribution.
Among the described step D, in the described control breaker, be installed on the high-speed rotary main shaft the multi-disc rotatable lamella and on a plurality of export-oriented cutter piece, the tubular framework of cutter piece periphery and the screen cloth of parcel vis-a-vis, do to relatively rotate at a high speed, to carry out fragmentation from the positive electrode that casing upper front end charging aperture enters the tubular framework, the mixed-powder that fragmentation obtains is from the collection of sieving of the powder discharging opening of bottom, casing stage casing.
Described control breaker comprises that the order number is 80 purpose screen clothes, described step e) in, adopt 100 purpose vibrating separating sieves, the aluminium matter particle that collection is obtained and the mixture of anodal powder carry out the meticulous sorting of sieving, and separate obtaining very high aluminium matter particle of purity and anodal powder.
Correspondingly, another correlation technique solution of the present invention is a kind of production system of the broken recovery method of control of waste battery as mentioned above that is used for, and described production system comprises.
A kind of being used for controlled broken recovery system as the waste battery of recovery method as described in one of claim 1-7, it comprises the waste battery sorting device that utilizes the physical property sorting, it is characterized in that: described recovery system also comprises battery rejuvenator, physical separation equipment, the control breaker of waste battery, vibrating separating sieve; Described waste battery sorting device, battery rejuvenator, physical separation equipment, described control breaker and vibrating separating sieve mainly advancing separately/discharging opening is connected in regular turn and directly or indirectly mutually; Described vibrating separating sieve adopts than the described control breaker screen cloth of the order of manying number more.
Therefore, system of the present invention adopts physical separation method substantially, but because separating mechanism and structure composition are more original, substantially do not adopt the soda acid chemicals, therefore, removal process can significantly reduce environmental pollution, approaching original 90% purity of cobalt acid lithium powder that separation process less energy intensive, final recovery obtain, thereby be more conducive to economical operation.
Reclaim automaticity and separative efficiency in order to improve to separate, be provided with gravity, vibrating transportation mechanism between described waste battery sorting device, battery rejuvenator, physical separation equipment, described control breaker and the vibrating separating sieve, be connected to keep technology each other; Described control breaker comprises that the order number is 80 purpose screen clothes, and described vibrating separating sieve adopts the screen cloth of 100 order numbers.
Reclaim automaticity and separative efficiency in order further to improve to separate, be provided with the power conveying mechanism between the coarse fodder discharging opening of described control breaker and the charging aperture, perhaps, described recovery system comprises two-stage or above control breaker, is provided with gravity or power conveying mechanism between the coarse fodder discharging opening of prime control breaker and the back level control breaker charging aperture.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is the structural representation of control breaker embodiment of the present invention.
Fig. 2 controls the structural representation of broken recovery system embodiment for the present invention.
Embodiment
Control broken recovery method embodiment:
Controlling broken recovery method embodiment for waste battery of the present invention comprises the steps:
A) waste battery is carried out sorting and grouping, described sorting and grouping is to adopt the combination of gravity, magnetic force, shape difference, four kinds of equipment of actinoscopy X to come dissimilar waste battery mixtures are carried out sorting and grouping.Collection obtains discarded lithium ion battery;
B) utilize the waste battery rejuvenator that the shell of lithium ion battery is carried out broken shell, described waste battery rejuvenator comprises the drive rod that is located at the protruding sword of battery shaft in nib, advances battery to move in axial nib.Collect after the broken shell and obtain the content of lithium ion battery, and metal or plastic casing are dealt with in addition;
C) the lithium ion battery content that collection is obtained is through physical separation, and described physical separation adopts gravity, magnetic force, wherein one or more combination of wind sorting equipment.Physical separation is collected and to be obtained aluminium matter positive plate and to adhere to anodal active coating on it, and the copper negative plate and the negative electrode active coating of adhering on it deal with in addition; With the copper negative plate that obtains and on the carbonaceous negative electrode active coating of adhering to, carry out wash-out and separate, then, the carbonaceous siccative sent reclaims heat energy in the stove, copper negative plate directly carries out commercial distribution;
D) the aluminium matter positive plate that collection is obtained and adhere to anodal active coating on it and send into the control breaker of waste battery and control fragmentation, in the described control breaker, be installed on the high-speed rotary main shaft the multi-disc rotatable lamella and on a plurality of export-oriented cutter piece, the tubular framework of cutter piece periphery and the screen cloth of parcel vis-a-vis, do to relatively rotate at a high speed, to carry out fragmentation from the positive electrode that casing upper front end charging aperture enters the tubular framework, the mixed-powder that fragmentation obtains is from the collection of sieving of the powder discharging opening of bottom, casing stage casing.The broken mixture that obtains aluminium matter particle and anodal powder of collecting of control; Described control breaker comprises that the order number is 80 purpose screen clothes;
E) adopt 100 purpose vibrating separating sieves, the aluminium matter particle that collection is obtained and the mixture of anodal powder carry out the meticulous sorting of sieving, and separate obtaining very high aluminium matter particle of purity and anodal powder.Carry out the purification of the commercial distribution or the degree of depth then respectively or handle reuse.
Control breaker embodiment:
As Fig. 1, be depicted as the structural representation of control breaker embodiment of the present invention.This breaker comprises support 10 and the horizontal tubular casing 20 that is installed on the support 10, offer charging aperture 21 on the described casing 20, discharging opening 22, also offer maintenance usefulness on casing 20 tops, hinged salable door leaf 23, in casing 20 inside, but the main shaft 30 of high speed rotating is installed by bearing 33, on this main shaft 30 and 3 rotatable lamellas 40 along described main shaft 30 vertical hard-wired rectangular frames are installed, in tubular casing 20 inside, periphery around described rotatable lamella 40 is equipped with framework 50 cylindraceous, and on described tubular framework 50 peripheries, be enclosed with screen cloth 51, at the cutter piece 42 that is fixed with a plurality of extroversions on the bridging beam 41 of crossing of this rotating frame 40, the inwall of the outer rim of described cutter piece 42 and described tubular framework 50 keeps suitable constant spacing; Described charging aperture 21 is located at casing 20 upper front end, and the bottom in described casing 20 stage casings offers powder discharging opening 22A.The bottom of described casing end also offers coarse fodder discharging opening 22B.
Hard-wired cutter piece 42 has airflow clearance each other on described bridging beam 41 excessively.
Crossing on the bridging beam 41 of each rotatable lamella 40, vertically, offer an exhaust discharge orifice (will not know clearly and show) according to certain spacing rule along it.
Near on the main shaft 30 of described charging aperture 21 charging exhauster(-tor 43 is being installed.
The described cutter piece 42 of every row is divided into many groups according to neighbouring relations, and every group of cutter piece 42 be linear array each other, two adjacent groups cutter piece 42 certain distance that staggers each other.
The order number of described screen cloth 51 is 80 orders; Described breaker comprises motor 31 and gearbox 32, and the rotating speed of described main shaft 30 is not less than 2000 commentaries on classics/per seconds.
Control broken recovery system embodiment:
As Fig. 2, be depicted as the structural representation that the present invention controls broken recovery system embodiment.It comprises the waste battery sorting device 100 that utilizes the physical property sorting, and it comprises the combination of gravity, magnetic force, shape difference, four kinds of equipment of actinoscopy X;
And described recovery system also comprises battery rejuvenator 200, and it comprises the drive rod that is located at the protruding sword of battery shaft in nib, advances battery to move in axial nib.Collect after the broken shell and obtain the content of lithium ion battery, and metal or plastic casing are dealt with in addition;
Physical separation equipment 300, it adopts the combination of gravity, wind sorting equipment.
The control breaker 400 of waste battery, vibrating separating sieve 500; Described waste battery sorting device 100, battery rejuvenator 200, physical separation equipment 300, described control breaker 400 and vibrating separating sieve 500 mainly advancing separately/discharging opening is connected in regular turn and directly or indirectly mutually; Described vibrating separating sieve 500 adopts than described control breaker 400 screen cloth of the order of manying number more.
Described recovery system comprises two-stage or above control breaker 400A, 400B, is provided with gravity or power conveying mechanism 600 (not shown) herein between the coarse fodder discharging opening 22B of prime control breaker 400A and the back level control breaker 400B charging aperture 21.The coarse fodder discharging opening 22B of back level control breaker 400B still has not broken on a small quantity thing to send prime control breaker 400A charging aperture 21 back to.
Be provided with gravity, vibrating transportation mechanism 600 between described waste battery sorting device 100, battery rejuvenator 200, physical separation equipment 300, described control breaker 400 and the vibrating separating sieve 500, keep technology each other to be connected; Described control breaker 400 comprises that the order number is 80 purpose screen clothes, and described vibrating separating sieve 500 adopts the screen cloth of 100 order numbers.Obtain the positive electrode active material powder of the aluminium flake particle that sieves and the sieve approaching original purity of cobalt acid lithium down respectively from vibrating separating sieve 500.Other separators such as negative material, housing separate more easily, and other deals with.

Claims (10)

1. the broken recovery method of the control of a waste battery, this recovery method comprises the steps: A) waste battery is carried out sorting and grouping, collect and obtain discarded lithium ion battery; B) utilize the waste battery rejuvenator that the shell of lithium ion battery is carried out broken shell, collects and obtain the content of lithium ion battery, and metal or plastic casing are dealt with in addition; C) the lithium ion battery content that collection obtained is through physical separation, collect to obtain aluminium matter positive plate and adhere to anodal active coating on it, and the copper negative plate and the negative electrode active coating of adhering on it deals with in addition; D) the aluminium matter positive plate that collection is obtained and adhere to anodal active coating on it and send into the control breaker of waste battery and control fragmentation is collected the mixture that obtains aluminium matter particle and anodal powder; E) the aluminium matter particle that collection is obtained and the mixture of anodal powder carry out the meticulous sorting of sieving, and aluminium matter particle that obtains respectively and anodal powder carry out the purification of the commercial distribution or the degree of depth then respectively or handle reuse.
2. the broken recovery method of the control of waste battery as claimed in claim 1, it is characterized in that: described steps A), described sorting and grouping be adopt gravity, magnetic force, shape difference, actinoscopy X equipment wherein one or more combination come dissimilar waste battery mixtures are carried out.
3. the broken recovery method of the control of waste battery as claimed in claim 1 is characterized in that: at described step B) in, described waste battery rejuvenator comprises the drive rod that is located at the protruding sword of battery shaft in nib, advances battery to move in axial nib.
4. the broken recovery method of the control of waste battery as claimed in claim 1 is characterized in that: at described step C) in, described physical separation adopts gravity, magnetic force, wherein one or more combination of wind sorting equipment.
5. the broken recovery method of the control of waste battery as claimed in claim 1, it is characterized in that: described step C), with the copper negative plate that obtains and on the carbonaceous negative electrode active coating of adhering to, carrying out wash-out separates, then, the carbonaceous siccative sent reclaim heat energy in the stove, copper negative plate directly carries out commercial distribution.
6. the broken recovery method of the control of waste battery as claimed in claim 1, it is characterized in that: described step D), in the described control breaker, be installed on the high-speed rotary main shaft the multi-disc rotatable lamella and on a plurality of export-oriented cutter piece, the tubular framework of cutter piece periphery and the screen cloth of parcel vis-a-vis, do to relatively rotate at a high speed, to carry out fragmentation from the positive electrode that casing upper front end charging aperture enters the tubular framework, the mixed-powder that fragmentation obtains is from the collection of sieving of the powder discharging opening of bottom, casing stage casing.
7. the broken recovery method of the control of waste battery as claimed in claim 1, it is characterized in that: described control breaker comprises that the order number is 80 purpose screen clothes, described step e) in, adopt 100 purpose vibrating separating sieves, the aluminium matter particle that collection is obtained and the mixture of anodal powder carry out the meticulous sorting of sieving, and separate obtaining very high aluminium matter particle of purity and anodal powder.
8. one kind is used for controlling broken recovery system as the waste battery of recovery method as described in one of claim 1-7, it comprises the waste battery sorting device that utilizes the physical property sorting, it is characterized in that: described recovery system also comprises battery rejuvenator, physical separation equipment, the control breaker of waste battery, vibrating separating sieve; Described waste battery sorting device, battery rejuvenator, physical separation equipment, described control breaker and vibrating separating sieve mainly advancing separately/discharging opening is connected in regular turn and directly or indirectly mutually; Described vibrating separating sieve adopts than the described control breaker screen cloth of the order of manying number more.
9. as waste battery recovery system as described in the claim 8, it is characterized in that: be provided with gravity, vibrating transportation mechanism between described waste battery sorting device, battery rejuvenator, physical separation equipment, described control breaker and the vibrating separating sieve, be connected to keep technology each other; Described control breaker comprises that the order number is 80 purpose screen clothes, and described vibrating separating sieve adopts the screen cloth of 100 order numbers.
10. as waste battery recovery system as described in the claim 8, it is characterized in that: be provided with the power conveying mechanism between the coarse fodder discharging opening of described control breaker and the charging aperture, perhaps, described recovery system comprises two-stage or above control breaker, is provided with gravity or power conveying mechanism between the coarse fodder discharging opening of prime control breaker and the back level control breaker charging aperture.
CNB2007101254895A 2007-12-24 2007-12-24 Method of controlling fragmentation and recovery of waste battery and system thereof Active CN100514745C (en)

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