CN102953081A - Method and system for respectively recycling tellurium and cadmium from module containing cadmium telluride - Google Patents
Method and system for respectively recycling tellurium and cadmium from module containing cadmium telluride Download PDFInfo
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- CN102953081A CN102953081A CN201110255648XA CN201110255648A CN102953081A CN 102953081 A CN102953081 A CN 102953081A CN 201110255648X A CN201110255648X A CN 201110255648XA CN 201110255648 A CN201110255648 A CN 201110255648A CN 102953081 A CN102953081 A CN 102953081A
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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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
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- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
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Abstract
The invention relates to a method for respectively recycling tellurium and cadmium from one or more modules containing cadmium telluride. The method comprises the following steps of: (a) placing the modules in an electrolyte; (b) depositing a first element of tellurium and cadmium in the electrolyte to a first working electrode; and (c) depositing a second element of tellurium and cadmium in the electrolyte to a second working electrode.
Description
Technical field
The present invention relates to from the module that contains cadmium telluride, reclaim respectively the method and system of tellurium and cadmium, be specifically related to from the discarded optoelectronic equipment that contains cadmium-telluride layer, reclaim respectively the method and system of tellurium and cadmium.The invention still further relates to the method and apparatus that from the discarded optoelectronic equipment that contains glass-base, cadmium-telluride layer and glass protecting cover layer, reclaims glass baseplate and/or glass protecting cover layer.
Background technology
Become more and more today of shortage in Nonrenewable resources, use the optoelectronic equipment of sustainable, reproducible cleaning sun power to become more and more welcome.Yet for the optoelectronic equipment that contains cadmium telluride, such as the cadmium telluride solar cell, tellurium wherein and cadmium have problem separately, and tellurium is rare especially metal, and cadmium is the very high carcinogens of toxicity of generally acknowledging.Therefore, from discarded cadmium telluride solar cell, such as, recovery tellurium and cadmium become a topical subject in the cadmium telluride photoelectric field in the waste material of the cadmium telluride solar cell that is finished or cadmium telluride manufacture of solar cells process.
The recovery method of using at present generally need will be discarded the crushing of cadmium telluride solar cell, allow cadmium telluride solar cell and acidifier and the oxidant reaction of crushing, again separation and collect respectively tellurium and cadmium.These methods generally include a lot of steps, so more complicated.In addition, these methods need the crushing of cadmium telluride solar cell, then reclaim only to account for from glass or plastic basis material＜metal of 0.05% mass percent, so are not very economicals.Such as, analyze from the cost efficiency of photoelectric field, with the method for cadmium telluride solar cell crushing so that the value that glass reclaims reduces not economical rationality widely.
The sulfuric acid ionogen that can be used as electrochemical cell is used for removing cadmium telluride from cadmium telluride solar cell waste material according to reports, and the ratio that regains cadmium and tellurium at an electrode of the concentration by regulating cadmium in voltage, stirring velocity and the ionogen that uses is the Cadimium telluride thin film from 1: 1 to 1: 6.This report is not described this experiment in detail and how to be carried out, so be difficult to copy this experiment.And the simulated experiment demonstration is difficult to obtain the cadmium telluride that can directly be used for producing the cadmium telluride solar cell.In addition, when attempting to reclaim tellurium separately in simulated experiment, pure tellurium can only obtain in the low pH value ionogen of narrow range, and this may be because tellurium and cadmium all exist with ionic condition in ionogen sulfuric acid, they have in the tendency of close condition deposit to the electrode, thereby mutually pollute.Especially when the ionic concn in the ionogen changed along with deposition process, the situation of pollution was more obvious.Usually be difficult in the industrial application electrolytical pH value is maintained in the very narrow scope, therefore be difficult to obtain the tellurium of reliable quality.
Therefore, be necessary to develop a kind of new method and system that from contain cadmium telluride assembly or device, reclaim tellurium and cadmium.
Summary of the invention
The invention provides a kind of new method and system that from contain cadmium telluride assembly or device, reclaim tellurium and cadmium.
One aspect of the present invention relates to a kind of method that is used for reclaiming respectively tellurium and cadmium from one or more modules that comprise cadmium telluride.The method may further comprise the steps: (a) module is placed electrolytic solution; (b) with the tellurium in the electrolytic solution and the first element deposition in the cadmium to the first job electrode; And (c) with on the tellurium in the electrolytic solution and the second element deposition to the second working electrode in the cadmium.
The present invention relates to a kind of system that reclaims respectively tellurium and cadmium from the module that comprises cadmium telluride on the other hand.This system comprises: the first electrochemical appliance, and it comprises placing the first electrolyzer of electrolytic solution and as tellurium deposited thereon first electrode of tellurium deposition plate to allow in the module; The second electrochemical appliance, it comprises placing the second electrolyzer of electrolytic solution and as cadmium deposited thereon second electrode of cadmium deposition plate to allow in the module; And the pH value controller, be used for controlling respectively and can realize selectivity deposition tellurium to a pH value of described the first electrode and can realize that selectivity deposition cadmium is to the 2nd pH value of described the second electrode.Wherein, described the first and second electrochemical appliances at least can so that the positions negotiable or the first and second electrodes of the electrolytic solution in described the first and second electrolyzers can exchange.
Method involved in the present invention has solved the technical problem of prior art.
Description of drawings
Fig. 1 has schematically shown among the embodiment and has made a module that comprises cadmium telluride with a device that comprises cadmium telluride, and this module has been positioned over the process of carrying out the selectivity deposition in the electrolyzer.
Fig. 2 has schematically shown a kind of system that is used for reclaiming respectively tellurium and cadmium from the module that comprises cadmium telluride among the embodiment.
Embodiment
Below will be described in detail the specific embodiment of the present invention.For fear of too much unnecessary details, in following content, will known structure or function be described in detail.
The language of approximation used herein can be used for quantitative expression, shows to allow quantity that certain change is arranged in the situation that does not change basic function.Therefore, with " approximately " " about " etc. the numerical value revised of language be not limited to this accurate numerical value itself.At least in some cases, the approximation language may be relevant with the precision of surveying instrument.Given numerical range can merge or mutually exchange herein, unless there is other Languages to limit in the literary composition, these scopes should comprise contained subrange in the scope.
Mentioned numerical value comprises from low to high all numerical value of the unit increase in a unit among the present invention, supposes at least two unit, interval between any lower value and the high value herein.For instance, if the quantity of a component or the value of a processing parameter, such as, temperature, pressure, time etc. is from 1 to 90,20 to 80 better, 30 to 70 the bests, to want to express being set forth in this specification sheets that 15 to 85,22 to 68,43 to 51,30 to 32 numerical value such as grade have all understood.For less than 1 numerical value, 0.0001,0.001,0.01 or 0.1 is considered to a more suitable unit.The aforementioned special example that will express of just hoping, all are regarded as clearly being listed as in this manual in a similar manner in the minimum combinations of values between maximum of enumerating.
One aspect of the present invention relates to a kind of method that is used for reclaiming respectively tellurium and cadmium from one or more modules that comprise cadmium telluride.The method may further comprise the steps: (a) module is placed electrolytic solution; (b) with the tellurium in the electrolytic solution and the first element deposition in the cadmium to the first job electrode; And (c) with on the tellurium in the electrolytic solution and the second element deposition to the second working electrode in the cadmium.
Can further comprise the pH value of regulating electrolytic solution in described step (b) with (c), be applied to the step of at least one parameter in the temperature of voltage on the electrode and electrolytic solution.In one embodiment, be used for making tellurium to deposit to a pH value on the working electrode and be controlled in the scope between 0 to 2.0 or 9.0 to 14.0, perhaps more appropriately, be controlled in the scope between 9.0 to 14.0; Be used for making cadmium to deposit to the 2nd pH value on the working electrode and be controlled in the scope between 6.0 to 8.5, perhaps more appropriately, be controlled in the scope between 7.0 to 8.5.
Described step (c) can be in described step (b) the deposition of the first element in tellurium and the cadmium proceed to a certain degree, implement when the current potential of described the first working electrode approaches the potential value that tends to the second element in codeposition tellurium and the cadmium.Described method can further comprise repeating step (b) and (c), until the tellurium in the described module and cadmium fully deposit to respectively on described the first and second working electrodes, such as, in one embodiment, but repeating step (b) and (c), until at least 95%, or more appropriately the tellurium of 99wt% mass percent deposits on described the first working electrode, or at least 95%, or more appropriately the cadmium of 99wt% mass percent deposits on described the second working electrode.
In certain embodiments, in described step (b) and deposition process (c), with other element outside the described module as described first job electrode or second working electrode to electrode.Described element with doing electrode can be the element that any electro-conductive material is made.Described electrolytic solution can comprise at least a in nitric acid and the sulfuric acid, and the cadmium telluride in the described module can incorporate in the described electrolytic solution before the deposition beginning.Such as, described electrolytic solution can be the solution of salpeter solution or sulfuric acid and hydrogen peroxide.
In further embodiments, in step (b), with described module itself as described first job electrode to electrode.
In one embodiment, in step (b), described module as described first job electrode to electrode, in step (c), described module again as described second working electrode to electrode.Such as, in a specific embodiment, module is placed the electrolytic solution in the electrolyzer, with its as the first job electrode that places this electrolytic solution to electrode, so that from the tellurium in the module and the first element in the cadmium, such as tellurium, deposit on the described first job electrode.In the process of the first element deposition in described tellurium and cadmium, the second element in described tellurium and the cadmium can increase gradually such as the concentration of cadmium in electrolytic solution.The deposition of the first element in described tellurium and cadmium was carried out after for some time, the current potential of described first job electrode approaches when tending to the potential value of the second element in codeposition tellurium and the cadmium, described first job electrode is replaced with second working electrode, regulate the pH of described electrolytic solution, put on the voltage of module and working electrode, and at least one parameter in the temperature of electrolytic solution, with described module as second working electrode to electrode so that described from the tellurium in the module and the second element deposition in the cadmium to described second working electrode.Then the deposition of the second element in described tellurium and cadmium was carried out after for some time, the current potential of described second working electrode approaches when tending to the potential value of the first element in codeposition tellurium and the cadmium, again described second working electrode replaced with the first job electrode, and corresponding adjusting deposition parameter, to realize the deposition of the first element in described tellurium and the cadmium.By such method, alternately tellurium and cadmium are deposited on the corresponding working electrode respectively fully.
In another embodiment, simultaneously at least two modules are deposited recovery tellurium and cadmium in the described method.Said method comprising the steps of: (a) the first module is placed the first electrolytic solution, the second module is placed the second electrolytic solution; (b) with described the first module as the tellurium working electrode to electrode, tellurium in described the first electrolytic solution is deposited on the described tellurium working electrode, with described the second module as the cadmium working electrode to electrode, the cadmium in described the second electrolytic solution is deposited on the described cadmium working electrode; (c) cadmium in described the first electrolytic solution is deposited on the described cadmium working electrode, the tellurium in described the second electrolytic solution is deposited on the described tellurium working electrode.
In described method, can further comprise the step that makes described the first and second electrolyte circulation or the position of described tellurium working electrode and cadmium working electrode is exchanged in step (b) with (c).
Exchanging of the circulation of described electrolytic solution or working electrode position can approach when tending to the potential value of codeposition cadmium at the current potential of described tellurium working electrode, or implements when the current potential of described cadmium working electrode approaches the potential value that tends to the codeposition tellurium.The current potential of working electrode can contrast a reference electrode, such as, the Ag/AgCl reference electrode is monitored.In one embodiment, the described potential value that tends to the codeposition cadmium is that relative Ag/AgCl reference electrode is approximately-value of 0.3V, and the described potential value that tends to the codeposition tellurium is to be approximately-value of 0.6V with respect to the Ag/AgCl reference electrode.Exchanging of the circulation of described electrolytic solution or working electrode position can reach at the current potential of the relative Ag/AgCl reference electrode of described tellurium working electrode-0.3V about, perhaps one approach-during the value of 0.3V but be higher than-0.3V, or reach at the current potential of the relative Ag/AgCl reference electrode of described cadmium working electrode-0.6V about, perhaps one approaches-implements during the value of 0.6V but be lower than-0.6V.In a specific embodiment, the current potential at the relative Ag/AgCl reference electrode of described tellurium working electrode exchanged of the circulation of described electrolytic solution or working electrode position reaches 0.15V to-0.3V, or more appropriately,-0.15V arrives-0.3V, or more appropriately,-0.15V is to 0.25V, or more appropriately, the value of-0.15V in the scope between the 0.2V, or reach at the current potential of the relative Ag/AgCl reference electrode of described cadmium working electrode-1.0V is to-0.6V, or more appropriately,-1.0V arrives-0.7V, or more appropriately ,-1.0V arrives-0.8V, or more appropriately ,-1.0V implements during a value in the scope the between-0.9V.
Described method can further comprise repeating step (b), until deposit to fully respectively on described tellurium working electrode and the cadmium working electrode from the tellurium in the first and second modules and cadmium.In one embodiment, described method further comprises repeating step (b), until from the tellurium of described the first and second modules or cadmium at least 95%, or preferably, till at least 99% mass percent has deposited on the corresponding working electrode.In addition, described method may further comprise repeating step (a) and (b), until the tellurium in described the first and second modules and cadmium fully deposit to respectively on described tellurium working electrode and the cadmium working electrode.When the metal level on depositing to tellurium working electrode and cadmium working electrode is enough thick, it can be scraped off from this working electrode, in order to recycle, can purify to it as required before reclaiming.
In one embodiment, described the first and second electrolytic solution are contained in respectively in the first and second electrolyzers, described the first and second electrolytic solution can circulate by the recycle pump that connects between described the first and second electrolyzers, with the concentration of metal ions in two electrolyzers of balance.In another embodiment, described the first and second electrolytic solution can be realized circulation by a storage container, such as, it can be realized by following steps: (i) electrolytic solution in described one of them electrolyzer is transferred to a storage container; (ii) electrolytic solution in another electrolyzer is transferred to describedly its electrolyte inside is transferred in the electrolyzer of storage container; And (iii) electrolytic solution in the described storage container is transferred to described another electrolyzer.
Described electrolytic solution can be any suitable solion, include but not limited to the amino iodate pyridine of salpeter solution, sulphuric acid soln, sodium hydroxide solution, metabisulfite solution, potassium sulfate solution, N-butyl-pyridinium a tetrafluoro borate, N-ethyl pyridinium bromide, 4-amidino pyridinium chloride, 3-amidino pyridinium chloride, 1-acetonyl pyridinium chloride and 1-.In one embodiment, the electrolytic solution of initial handling is different electrolytic solution in described the first and second electrolyzers.In another embodiment, described the first and second electrolyzer initial handlings is the different same electrolytic solution of pH value.
Described working electrode can be fit to make the material of working electrode to use by any in electrolytic solution.Can include but not limited at least a in transparent conductive oxide (TCO) glass, platinum, graphite, copper, aluminium and the iron such as, described working electrode.In one embodiment, described tellurium working electrode is different from described cadmium working electrode.In another embodiment, described tellurium working electrode is identical with described cadmium working electrode.
Described method can comprise further that respectively control realizes the tellurium selectivity is deposited to a pH value of described tellurium working electrode and the 2nd pH value that realization deposits to the cadmium selectivity described cadmium working electrode.In one embodiment, the described step of controlling respectively the first and second pH values comprises: control respectively the pH value in the first and second electrolyzers when the deposition beginning, and in deposition process, the circulation of electrolytic solution or exchanging of tellurium working electrode and cadmium working electrode position in corresponding each the first and second electrolyzers, pH value in corresponding adjustment the first and second electrolyzers, guaranteeing that the pH value in the electrolyzer of implementing tellurium deposited on the tellurium working electrode remains a pH value, and the pH value in enforcement deposits to cadmium electrolyzer on the cadmium working electrode remains the 2nd pH value.In one embodiment, a described pH value approximately is controlled in 0 to 2.0 or 9.5 to 14.0 the scope, or more appropriately, approximately is controlled in 12.0 to 14.0 the scope; Described the 2nd pH value approximately is controlled in 6.0 to 8.5 the scope, or more appropriately, approximately is controlled in 7.0 to 8.5 the scope.
Described method can further comprise control respectively one be suitable for selectivity deposition tellurium to the tellurium working electrode the first deposition voltage and be suitable for second deposition voltage of selectivity deposition cadmium to the cadmium working electrode.In one embodiment, the described step of controlling respectively the first and second deposition voltages comprises: the deposition voltage that will be applied on the tellurium working electrode remains the first deposition voltage, and the deposition voltage that is applied to the cadmium working electrode remains the second deposition voltage.In one embodiment, described the first deposition voltage greatly about-2.5V in the scope of 0V, described the second deposition voltage greatly about-2.5V in the scope of 0V.Described the first and second deposition voltages may identical also possibility difference.
In described method, can increase by various means the selectivity of tellurium deposition or cadmium deposition.
In certain embodiments, described module is the device that comprises cadmium telluride by a kind of, such as formation such as useless optoelectronic equipments.Can produce the module that is applicable to described method by a kind of device of cadmium telluride that comprises by the following method, that is: the part that contains cadmium telluride of this device is exposed to outside, or outside its adjacent part that contains the part of cadmium telluride is exposed to, when it is positioned over when depositing in the electrolytic solution, this adjacent part solubilized makes electrolytic solution can act on the described part that contains cadmium telluride in electrolytic solution.The described adjacent part that contains the part of cadmium telluride can be dissolved in the electrolytic solution with the described part that contains cadmium telluride, also can contain being partly dissolved in the electrolytic solution of cadmium telluride prior to described.
In one embodiment, described module is from a device that comprises glass-base, glass protecting cover layer and the cadmium-telluride layer between this glass-base and glass protecting cover layer, can remove in a certain way to form described module by the glass protecting cover layer with device, the described mode that removes makes still recyclable recycling of described glass protecting cover layer.In one embodiment, after tellurium thereon and cadmium deposit on the corresponding working electrode fully, the glass-base of described the first and second modules does not have machinery, physics or infringement chemically substantially, entirely recycling, or recycling after passing through certain polishing or revising operation.Described glass protecting cover layer or glass-base, perhaps may be through polishing or revised glass protecting cover layer or glass-base, can after through certain mist agent or organic solution cleaning, recycle, wherein suitable organic solution includes but not limited to acetone, ethanol, methyl alcohol etc., and suitable inorganic solution includes but not limited to nitric acid, sulfuric acid, hydrochloric acid etc.
In a specific embodiment, described device comprises glass-base, oxidic, transparent, conductive layers, cadmium sulfide layer, cadmium-telluride layer, sealing material layer and glass protecting cover layer successively, heat this device make its sealing material melting layer or burn after again its glass protecting cover layer is removed, just can obtain described module.In the process of deposition, described cadmium sulfide layer and cadmium-telluride layer are dissolved in the electrolytic solution, and described oxidic, transparent, conductive layers and described glass-base remain unchanged substantially, after by methods such as polishings described oxidic, transparent, conductive layers being removed, and the recyclable recycling of described glass-base.The described removal recycles after the glass-base behind the oxidic, transparent, conductive layers can clean with aforementioned organic or inorganic solution.
For instance, in the described embodiment of Fig. 1, module 150 is from a discarded optoelectronic equipment 100, this device 100 comprises glass-base 102, oxidic, transparent, conductive layers 104, Cadmium Sulfide transition layer 106, cadmium telluride absorption layer 108, graphite (metal) conductive layer 110 and glass protecting cover layer 112 successively, and wherein said glass protecting cover layer 112 is to adhere on described graphite (metal) conductive layer 110 by adhesive seal material (not shown).Described module 150 falls described adhesive seal material combustion by heating described device 100, then removes described glass protecting cover layer 112, is exposed to described conductive layer 110 outer and forms.Then described module 150 is positioned in the electrolyzer 200 that contains electrolytic solution, be used as one to electrode, described graphite (metal) conductive layer 110 on it can be dissolved in the electrolytic solution with cadmium telluride absorption layer 108 and Cadmium Sulfide transition layer 106, and tellurium and/or cadmium in the electrolytic solution are deposited on the working electrode 205 that is positioned in the electrolyzer 200.
As shown in Figure 2, in illustrated embodiment, provide a kind of system 300 that comprises two electrochemical appliances, be used for from the module that comprises cadmium telluride, reclaiming respectively tellurium and cadmium.Described system 300 comprises the first electrochemical appliance 302 and the second electrochemical appliance 308, wherein said the first electrochemical appliance 302 comprise placing the first electrolyzer 304 of electrolytic solution and as the tellurium deposition plate allowing tellurium in the module deposit the first electrode 306 on it, described the second electrochemical appliance 308 comprise placing the second electrolyzer 310 of electrolytic solution and as the cadmium deposition plate to allow cadmium in the module deposit the second electrode 312 on it.Described system 300 also comprises pH value controller 314, is used for controlling respectively can realizing selectivity deposition tellurium to a pH value of described the first electrode 306 and can realizing that selectivity deposition cadmium is to the 2nd pH value of described the second electrode 312.
The first module 402 and the second module 404 are positioned over respectively the first electrolyzer 304 and the second electrolyzer 310.Electrolytic solution in described the first electrolyzer is controlled in a pH value that is beneficial to selectivity deposition tellurium, and the electrolytic solution in described the second electrolyzer is controlled in the 2nd a pH value that is beneficial to selectivity deposition cadmium.Between described the first module 402 and the first electrode 306, apply the first voltage difference by a voltage-operated device (not shown), it is poor to apply second voltage between described the second module 404 and the second electrode 312, described as the tellurium working electrode the first electrode 306 and comprise respectively as the chemical reaction on the first module 402 of electrode of tellurium working electrode:
On the first module: CdTe-6e
-→ Cd
2++ Te
4+
Te
2--2e
-→Te-2e
-→Te
2+-2e
-→Te
4+
On the first electrode: HTeO
2 ++ 3H
++ 2e
-→ Te
2++ 2H
2O (PH＞=7);
TeO
3 2-+3H
2O+2e
-→Te
2++6OH
-
Te
2++2e
-→Te
Described as the cadmium working electrode the second electrode 312 and be respectively as the chemical reaction on the second module 404 of electrode of cadmium working electrode:
On the second module: CdTe-6e
-→ Cd
2++ Te
4+
On the second electrode: Cd
2++ 2e
-→ Cd
Like this, cadmium telluride on the first module 402 is dissolved in the electrolytic solution in the first electrolyzer 304, tellurium wherein is deposited on the first electrode 306, and the cadmium telluride on the second module 404 is dissolved in the electrolytic solution in the second electrolyzer 310, and cadmium wherein is deposited on the second electrode 312.
In certain embodiments, reaction conditions in described each electrochemical appliance, such as the pH value of temperature, electrolytic solution, put on voltage difference on module and the electrode etc. and can suitably regulate according to practical situation, being beneficial to cadmium telluride is dissolved down from module, tellurium and cadmium deposit to electrode and get on, and Reaction time shorten etc.
In illustrated embodiment, described the first electrolyzer 304 be connected electrolyzer 310 and be connected connection with pump by pipeline 316, to realize the electrolyte circulation between described the first and second electrolyzers 304 and 310.When reclaiming, the deposition of the first electrolyzer 304 interior telluriums proceeds to a certain degree, its current potential is during near a value that is conducive to the codeposition cadmium, perhaps wait the deposition recovery of two electrolyzers, 310 interior cadmiums to proceed to a certain degree, its current potential is during near a value that is conducive to the codeposition tellurium, can realize by pump 318 circulation of the electrolytic solution in described the first and second electrolyzers, so that the homogenizing of concentration of metal ions in two electrolyzers.In another embodiment, described system 300 may comprise a storage container, is used in the process that electrolytic solution in described the first and second electrolyzers circulates, the interim electrolytic solution that discharges in one of them electrolyzer of placing.
In some other embodiment, the setting of described the first electrochemical appliance 302 and the second electrochemical appliance 308 can realize the exchange of the electrode in described the first electrolyzer 304 and the second electrolyzer 310, like this, when reclaiming, the deposition of the first electrolyzer 304 interior telluriums proceeds to a certain degree, its current potential is during near a value that is conducive to the codeposition cadmium, perhaps wait the deposition recovery of the cadmium in two electrolyzers 310 to proceed to a certain degree, its current potential is during near a value that is conducive to the codeposition tellurium, described the first electrode 306 and the second electrode 312 capable of interchanging positions.
Described method and system provided by the present invention can also be applicable to copper-indium-galliun-selenium film solar cell.
Following instance only is to provide certain guidance for those skilled in the art implement the invention that claim protects, and therefore, these examples should not limit claims scope required for protection.
Experiment in the following instance is finished with other equipment of laboratory-scale.
Example one
This experiment has been adopted and has a kind ofly been combined the system that comprises two electrochemical appliances that Fig. 2 is described carry out the recovery of tellurium and cadmium in preamble.
This experiment has adopted a CHI660D type electrochemistry worktable (available from Chinese Shanghai occasion China Instr Ltd.) to apply the reaction times of voltage and control experiment.
With two laminar cadmium telluride solar panels (available from First Solar, Inc., FS-272,72.5W) about 10 minutes of 450 ℃ of heating, remove its glass protecting cover layer, outside its metal conducting layer near the cadmium telluride absorption layer is exposed to, form the first and second cadmium telluride modules.
The first platinum foil is put into described the first electrolyzer it is contacted with electrolytic solution, take it as the tellurium working electrode (tellurium deposition plate); Described the first cadmium telluride module is put into the first electrolyzer it is contacted with electrolytic solution, take it as described tellurium working electrode to electrode.The second platinum foil is put into described the secondth electrolyzer it is contacted with electrolytic solution, take it as cadmium electrode (cadmium deposition plate); Described the second cadmium telluride module is put into the second electrolyzer it is contacted with electrolytic solution, take it as described cadmium working electrode to electrode.
Electrolytic solution in described the first electrolyzer is controlled in one and is suitable for the tellurium selectivity is deposited to a pH value on described the first platinum foil, and the electrolytic solution in described the second electrolyzer is controlled in one and is suitable for the cadmium selectivity is deposited to the 2nd pH value on described the second platinum foil.By the electrochemistry worktable, can between described the first cadmium telluride module and the first platinum foil, apply first voltage difference to realize electrolysis, so that be deposited on described the first platinum foil from the tellurium on described the first cadmium telluride module; And it is poor to realize electrolysis, so that be deposited on described the second platinum foil from the cadmium on described the second cadmium telluride module to apply a second voltage between described the second cadmium telluride module and the second platinum foil.
When the current potential of tellurium working electrode (the first platinum foil) during near a value of tending to the codeposition cadmium, or when the current potential of cadmium working electrode (the second platinum foil) during near a value of tending to the codeposition tellurium, the position of described the first platinum foil and the second platinum foil is exchanged, be about to the first platinum foil and be transferred to the second electrolyzer, the second platinum foil is transferred to the first electrolyzer.
Then the pH value in the first electrolyzer is adjusted to the 2nd pH value, the pH value in the second electrolyzer is adjusted to a pH value.It is poor to apply second voltage between described the first cadmium telluride module and the second platinum foil, so that be deposited on described the second platinum foil from the cadmium on described the first cadmium telluride module; And between described the second cadmium telluride module and the first platinum foil, apply the first voltage difference, so that be deposited on described the first platinum foil from the tellurium on described the second cadmium telluride module.
Can repeatedly repeat described current potential at tellurium working electrode (the first platinum foil) and exchange the position of the first and second platinum foils near the current potential of a value of tending to the codeposition cadmium or cadmium working electrode (the second platinum foil) during near a value of tending to the codeposition tellurium, and the step of the value of corresponding adjusting/control pH value and voltage difference, until the tellurium on described the first and second cadmium telluride modules and cadmium deposit to respectively on described the first and second platinum foils fully.
After electrolytic deposition is finished, utilize energy spectrometer and/or Inductive Coupled Plasma Emission Spectrometer ICP to analyze being deposited on the material that deposits on described the first and second platinum foils, record the mass percent of cadmium on the mass percent of tellurium on the first platinum foil and the second platinum foil.
In described the first and second electrolyzers, all use sodium sulfate (analyzing flow 0.2M, available from chemical reagent Shanghai company limited of traditional Chinese medicines group) to carry out series of experiments for electrolytic solution.Wherein, the pH value of electrolytic solution is regulated with sulfuric acid or sodium hydroxide, and can increase with silicone oil bath the temperature of electrolytic solution, makes it be higher than room temperature.
Parameter in described series of experiments comprises that the pH value of the temperature of the voltage difference that puts on electrode, electrolytic solution and electrolytic solution is as shown in table 1 below.Described experiment used finish in about 5 hours.In each experiment that obtains by Inductive Coupled Plasma Emission Spectrometer ICP on the first platinum foil on the mass percent of tellurium and the second platinum foil mass percent such as the following table 1 of cadmium show.
Table 1
As shown in table 1, when a pH value that is fit to the tellurium deposition less than 2.1 or greater than 9, the 2nd pH value that is fit to the cadmium deposition is between 6.0 to 8.5 the time, obtain respectively on tellurium deposition plate and the cadmium deposition plate highly purified tellurium (such as, up to 100wt%) and highly purified cadmium (such as, up to 96.5wt%).
Example two
A cadmium telluride module is positioned over the cadmium telluride that makes in the electrolytic solution wherein to be dissolved in this electrolytic solution, setting comprises electrolyte ph, put on the deposition parameter of the temperature of the voltage (or sedimentation potential) of electrode and electrolytic solution, so that the first element (tellurium or cadmium) in tellurium and the cadmium deposits on first working electrode in the described electrolytic solution.The deposition of the first element in described tellurium and cadmium was carried out after for some time, described the first working electrode is replaced to the second working electrode, and corresponding adjusting deposition parameter, the second element (cadmium or tellurium) in the tellurium and cadmium deposits on described the second working electrode in the electrolytic solution so that state.
Reference electrode, be respectively the first and second working electrodes with the first and second platinum electrodes, take the 3rd platinum electrode as the first or second working electrode to electrode, the sedimentation potential between control working electrode and the reference electrode, and surveying work electrode and to the deposition current between the electrode.Take salpeter solution as electrolytic solution, so that cadmium telluride is with Cd
2+And HTeO
2+Form be dissolved in wherein.Can improve or reduce by adding nitric acid or sodium hydroxide the pH value of described salpeter solution.
Implemented two groups of experiments by first the tellurium in the salpeter solution being deposited to the first working electrode and then the cadmium in the salpeter solution being deposited to the second working electrode, its experiment parameter is as shown in table 2 below.In each experiment that obtains by Inductive Coupled Plasma Emission Spectrometer ICP on the first working electrode on the mass percent of tellurium and the second working electrode mass percent such as the following table 2 of cadmium show.
Table 2
Implemented two groups of experiments by first the cadmium in the salpeter solution being deposited to the second working electrode and then the tellurium in the salpeter solution being deposited to the first working electrode, its experiment parameter is as shown in table 3 below.In each experiment that obtains by Inductive Coupled Plasma Emission Spectrometer ICP on the second working electrode on the mass percent of cadmium and the first working electrode mass percent such as the following table 3 of tellurium show.
Table 3
Shown in table 2 and 3, by under suitable pH value and sedimentation potential, alternately tellurium and cadmium being deposited to respectively the method on the first and second working electrodes, can obtain highly purified tellurium and cadmium, such as, the pH value be 0 and the suitable situation of current potential under, can deposit and obtain highly purified tellurium, again the pH value is transferred to about 8.5, under a suitable current potential, can obtain highly purified cadmium again.
Although in embodiment, Partial Feature of the present invention is had been described in detail and describes, under the prerequisite that does not break away from spirit of the present invention, can carry out various changes and replacement to the present invention.Same, those skilled in the art also can obtain other change disclosed by the invention and equivalent according to normal experiment.All these change, and replacement and equivalent are all within the design and scope of the defined claim of the present invention.
Claims (25)
1. method that is used for from one or more modules that comprise cadmium telluride, reclaiming respectively tellurium and cadmium, the method comprises:
(a) module is placed electrolytic solution;
(b) with the tellurium in the electrolytic solution and the first element deposition in the cadmium to the first job electrode; And
(c) with on the tellurium in the electrolytic solution and the second element deposition to the second working electrode in the cadmium.
2. the method for claim 1 further comprises the pH value of regulating electrolytic solution, is applied to the step of at least one parameter in the temperature of voltage on the electrode and electrolytic solution in described step (b) with (c).
3. the method for claim 1 further comprises repeating step (b) and (c), until have the tellurium of at least 95% mass percent or cadmium to deposit on the described working electrode.
4. the method for claim 1, in described step (b) and (c) with other element outside the described module as described first job electrode or second working electrode to electrode.
5. method as claimed in claim 4, wherein said electrolytic solution comprise at least a in nitric acid and the sulfuric acid, and the cadmium telluride in the described module incorporated in the described electrolytic solution before deposition.
6. the method for claim 1, in the deposition process of described step (b) with described module as described first job electrode to electrode.
7. method as claimed in claim 6, in the deposition process of described step (c) with described module as described second working electrode to electrode.
8. method as claimed in claim 6, wherein said module comprises glass-base and cadmium-telluride layer, but the depositional mode of described tellurium and cadmium is so that described glass-base recycled in its entirety.
9. method as claimed in claim 8, wherein said device comprises glass-base, transparent conductive oxide layer, cadmium sulfide layer, cadmium-telluride layer, sealing material layer and glass protecting cover layer successively, wherein said module be the described device of heating with its sealing material melting layer or burning, again glass protecting cover layer is removed rear formation.
10. method as claimed in claim 9, it comprises:
In described deposition process, described cadmium sulfide layer and cadmium-telluride layer are melted in electrolytic solution, and keep described glass-base and transparent conductive oxide layer substantially constant;
After described deposition is finished, described transparent conductive oxide layer is removed from described glass-base; And
Reclaim described glass-base.
11. method as claimed in claim 6, wherein, described step (a) comprising: the first module is placed the first electrolytic solution, the second module is placed the second electrolytic solution; Described step (b) comprising: with described the first module as the tellurium working electrode to electrode, tellurium in described the first electrolytic solution is deposited on the described tellurium working electrode, with described the second module as the cadmium working electrode to electrode, the cadmium in described the second electrolytic solution is deposited on the described cadmium working electrode; Described step (c) comprising: the cadmium in described the first electrolytic solution is deposited on the described cadmium working electrode, the tellurium in described the second electrolytic solution is deposited on the described tellurium working electrode.
12. method as claimed in claim 11 further comprises the step that makes described the first and second electrolyte circulation or described tellurium working electrode and cadmium working electrode are exchanged in described step (b) with (c).
13. method as claimed in claim 12, when the current potential of the relative Ag/AgCl reference electrode of described tellurium working electrode reaches 0.15V to a value between the scope of-0.3V, or reach at the current potential of the relative Ag/AgCl reference electrode of described cadmium working electrode-1.0V extremely-carry out the described step that makes electrolyte circulation or working electrode is exchanged during a value between the scope of 0.6V.
14. method as claimed in claim 12 further comprises repeating said steps (b) to (c), until have at least the tellurium of 95% mass percent or cadmium to deposit on the working electrode.
15. method as claimed in claim 14 comprises that further repeating step (a) is to (c).
16. method as claimed in claim 12, wherein said the first and second electrolytic solution place respectively two electrolyzers, and the described step that makes electrolyte circulation is to realize by the circulation pump that is connected between described two electrolyzers.
17. method as claimed in claim 12, wherein said the first and second electrolytic solution place respectively two electrolyzers, and the described step of electrolyte circulation that makes comprises: (i) electrolytic solution in one of them electrolyzer is moved on to a storage container; (ii) electrolytic solution in another electrolyzer is moved on to describedly its electrolyte inside is moved on in the electrolyzer of storage container; And (iii) electrolytic solution in the described storage container is moved on to described another electrolyzer.
18. method as claimed in claim 12, (c) further comprises before in described step: the corresponding described step that makes the first and second electrolyte circulation or tellurium working electrode and cadmium working electrode are exchanged, is applied to working electrode and to the step of at least one parameter in the temperature of the voltage on the electrode, electrolytic solution at the pH value of corresponding adjusting electrolytic solution.
19. the method for claim 1, wherein be used for making tellurium to deposit to a pH value on the tellurium working electrode and be controlled in the scope between 0 to 2.0 or between 9.0 to 14.0, and be controlled in the scope between 6.0 to 8.5 for making cadmium deposit to the 2nd pH value on the cadmium working electrode.
20. method as claimed in claim 19, a wherein said pH value are controlled in the scope between 12.0 to 14.0, described the 2nd pH value is controlled in the scope between 7.0 to 8.5.
21. a system of distinguishing tellurium and cadmium from the module that comprises cadmium telluride, this system comprises:
The first electrochemical appliance, it comprises placing the first electrolyzer of electrolytic solution and as tellurium deposited thereon first electrode of tellurium deposition plate to allow in the module;
The second electrochemical appliance, it comprises placing the second electrolyzer of electrolytic solution and as cadmium deposited thereon second electrode of cadmium deposition plate to allow in the module; And
The pH value controller is used for controlling respectively and can realizes selectivity deposition tellurium to a pH value of described the first electrode and can realize that selectivity deposition cadmium is to the 2nd pH value of described the second electrode;
Wherein, described the first and second electrochemical appliances at least can so that the positions negotiable or the first and second electrodes of the electrolytic solution in described the first and second electrolyzers can exchange.
22. system as claimed in claim 21, wherein said the first and second electrolyzers are connected with pump by pipeline, when being mounted with electrolytic solution in described the first and second electrolyzers, described pipeline and pump are so that the electrolytic solution in described the first and second electrolyzers can be realized regular or irregular circulation.
23. system as claimed in claim 21 further comprises storage container, carries out being used for placing the electrolytic solution of emitting in the process of electrolyte circulation from one of them electrolyzer between described the first and second electrolyzers.
24. system as claimed in claim 21 further comprises voltage-operated device, is used for controlling respectively the second voltage that can realize that tellurium deposited to the first voltage on described the first electrode and can realize cadmium is deposited to described the second electrode.
25. system as claimed in claim 21 further comprises monitoring device, is used for monitoring tellurium at least one in described the first and second electrolyzers or the concentration of cadmium.
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| CN103866129A (en) * | 2014-03-12 | 2014-06-18 | 中国科学院电工研究所 | Recycling method of CdTe solar cell module |
| CN105862059A (en) * | 2016-05-12 | 2016-08-17 | 中南大学 | Method for recovering tellurium through cyclone electrolysis of solution containing tellurium |
| CN110819807A (en) * | 2019-08-23 | 2020-02-21 | 中国东方电气集团有限公司 | Recovery system and method for mercury cadmium telluride material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103866129A (en) * | 2014-03-12 | 2014-06-18 | 中国科学院电工研究所 | Recycling method of CdTe solar cell module |
| CN103866129B (en) * | 2014-03-12 | 2016-01-20 | 中国科学院电工研究所 | A kind of recovery method of CdTe solar module |
| CN105862059A (en) * | 2016-05-12 | 2016-08-17 | 中南大学 | Method for recovering tellurium through cyclone electrolysis of solution containing tellurium |
| CN110819807A (en) * | 2019-08-23 | 2020-02-21 | 中国东方电气集团有限公司 | Recovery system and method for mercury cadmium telluride material |
| CN110819807B (en) * | 2019-08-23 | 2021-03-19 | 中国东方电气集团有限公司 | Recovery system and method for mercury cadmium telluride material |
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