CN102953081B - From containing the method and system reclaiming tellurium and cadmium the module of cadmium telluride respectively - Google Patents
From containing the method and system reclaiming tellurium and cadmium the module of cadmium telluride respectively Download PDFInfo
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- CN102953081B CN102953081B CN201110255648.XA CN201110255648A CN102953081B CN 102953081 B CN102953081 B CN 102953081B CN 201110255648 A CN201110255648 A CN 201110255648A CN 102953081 B CN102953081 B CN 102953081B
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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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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The present invention relates to a kind of being used for and comprise from one or more the method reclaiming tellurium and cadmium the module of cadmium telluride respectively.The method comprises the following steps: module is placed in electrolytic solution by (a); (b) by the tellurium in electrolytic solution and the first element deposition in cadmium on first job electrode; And (c) by the tellurium in electrolytic solution and the second element deposition in cadmium on second working electrode.
Description
Technical field
The present invention relates to for from containing the method and system reclaiming tellurium and cadmium in the module of cadmium telluride respectively, be specifically related to for from containing the method and system reclaiming tellurium and cadmium in the discarded optoelectronic equipment of cadmium-telluride layer respectively.The invention still further relates to the method and apparatus reclaiming glass baseplate and/or glass protecting cap layer from the discarded optoelectronic equipment containing glass-base, cadmium-telluride layer and glass protecting cap layer.
Background technology
Become today of more and more shortage in Nonrenewable resources, use the optoelectronic equipment of sustainable, reproducible clean sun power to become more and more welcome.But, for the optoelectronic equipment containing cadmium telluride, such as cadmium telluride solar cell, tellurium wherein and cadmium have respective problem, and tellurium is metal rare especially, and the cadmium carcinogens that to be generally acknowledged toxicity very high.Therefore, from discarded cadmium telluride solar cell, such as, reclaim tellurium and cadmium in the waste material of the cadmium telluride solar cell be finished or cadmium telluride manufacture of solar cells process and become a topical subject in cadmium telluride photovoltaic field.
The recovery method used at present generally need crush by discarded cadmium telluride solar cell, allows the cadmium telluride solar cell and acidifier and oxidant reaction that crush, then is separated and collection tellurium and cadmium respectively.These methods generally include a lot of step, therefore more complicated.In addition, cadmium telluride solar cell need crush by these methods, from glass or plastic basis material, then reclaim the metal only accounting for < 0.05% mass percent, is not therefore very economical.Such as, analyze from the cost efficiency of photoelectric field, the value that the method that cadmium telluride solar cell crushes makes glass reclaim is reduced widely, inadequate economical rationality.
Sulfuric acid can be used for removing cadmium telluride from cadmium telluride solar cell waste material as the ionogen of electrochemical cell according to reports, and is the Cadimium telluride thin film from 1: 1 to 1: 6 by the ratio regulating the concentration of cadmium in the voltage of use, stirring velocity and ionogen to regain cadmium and tellurium on one of the electrodes.This report is not described this experiment in detail and how to be carried out, so be difficult to copy this experiment.And simulated experiment display is difficult to obtain the cadmium telluride that can directly be used for producing cadmium telluride solar cell.In addition, when attempting to reclaim separately tellurium 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 the tendency deposited under close condition on electrode, thus mutually pollute.Especially, when the ionic concn in ionogen changes along with deposition process, the situation of pollution is more obvious.Usually be difficult to electrolytical pH value to maintain in very narrow scope in industrial application, be therefore difficult to the tellurium obtaining reliable quality.
Therefore, be necessary to develop a kind of newly from containing the method and system reclaiming tellurium and cadmium cadmium telluride assembly or device.
Summary of the invention
The invention provides a kind of newly from containing the method and system reclaiming tellurium and cadmium cadmium telluride assembly or device.
One aspect of the present invention relates to a kind of being used for and comprises from one or more the method reclaiming tellurium and cadmium the module of cadmium telluride respectively.The method comprises the following steps: module is placed in electrolytic solution by (a); (b) by the tellurium in electrolytic solution and the first element deposition in cadmium on first job electrode; And (c) by the tellurium in electrolytic solution and the second element deposition in cadmium on second working electrode.
The present invention relates to a kind of system reclaiming tellurium and cadmium from the module comprising cadmium telluride respectively on the other hand.This system comprises: the first electrochemical appliance, and it comprises the first electrolyzer for placing electrolytic solution and is used as tellurium deposition plate with the first electrode making the tellurium in module deposited thereon; Second electrochemical appliance, it comprises the second electrolyzer for placing electrolytic solution and is used as cadmium deposition plate with the second electrode making the cadmium in module deposited thereon; And pH value controller, be used for controlling respectively realizing selectivity deposition tellurium to the first pH value of described first electrode with selectivity can be realized deposit second pH value of cadmium to described second electrode.Wherein, described first and second electrochemical appliances at least can make the position that is negotiable or the first and second electrodes of the electrolytic solution in described first and second electrolyzers to exchange.
Method involved in the present invention solves the technical problem of prior art.
Accompanying drawing explanation
Fig. 1 show schematically show the device comprising cadmium telluride with in an embodiment and makes the module that comprises cadmium telluride, and this module is positioned over the process of carrying out selectivity deposition in electrolyzer.
Fig. 2 show schematically show a kind of system being used for reclaiming respectively tellurium and cadmium from the module comprising cadmium telluride in an embodiment.
Embodiment
Below will be described in detail the specific embodiment of the present invention.In order to avoid too much unnecessary details, will known structure or function be described in detail in following content.
The language of approximation used herein can be used for quantitative expression, shows to allow quantity to have certain variation when not changing basic function.Therefore, this exact value itself is not limited to the numerical value that the language such as " approximately " " left and right " are revised.At least in some cases, approximating language may be relevant with the precision of surveying instrument.Numerical range given herein can merge or mutually exchange, unless there is other Languages to limit in literary composition, these scopes should comprise subrange contained in scope.
Numerical value mentioned in the present invention comprises all numerical value that unit unit from low to high increases, and supposes at least two, interval unit between any lower value and high value herein.For example, if the quantity of a component or the value of a processing parameter, such as, temperature, pressure, time etc. is from 1 to 90, and 20 to 80 is better, and 30 to 70 is best, be think numerical value such as expression 15 to 85,22 to 68,43 to 51,30 to 32 grade all understand enumerate in this description.For the numerical value being less than 1,0.0001,0.001,0.01 or 0.1 is considered to a more suitable unit.Aforementionedly just hope the special example that will express, all minimum combinations of values between maximum enumerating all are regarded as clearly arranging in this manual in a similar manner.
One aspect of the present invention relates to a kind of being used for and comprises from one or more the method reclaiming tellurium and cadmium the module of cadmium telluride respectively.The method comprises the following steps: module is placed in electrolytic solution by (a); (b) by the tellurium in electrolytic solution and the first element deposition in cadmium on first job electrode; And (c) by the tellurium in electrolytic solution and the second element deposition in cadmium on second working electrode.
The step regulating the pH value of electrolytic solution, be applied at least one parameter in the temperature of voltage on electrode and electrolytic solution can be comprised further between described step (b) and (c).In one embodiment, be controlled in the scope between 0 to 2.0 or 9.0 to 14.0 for the first pH value making tellurium deposit on working electrode, or more appropriately, be controlled in the scope between 9.0 to 14.0; The second pH value for making cadmium deposit on working electrode is controlled in the scope between 6.0 to 8.5, or more appropriately, is controlled in the scope between 7.0 to 8.5.
Described step (c) can the deposition of the first element in the described step (b) in tellurium and cadmium proceed to a certain degree, and the current potential of described first working electrode is implemented close to when tending to the potential value of the second element in codeposition tellurium and cadmium.Described method can comprise repeating step (b) and (c) further, until tellurium in described module and cadmium fully deposit on described first and second working electrodes respectively, such as, in one embodiment, can repeating step (b) and (c), until at least 95%, or the tellurium of more appropriately 99wt% mass percent deposits on described first working electrode, or at least 95%, or the cadmium of more appropriately 99wt% mass percent deposits on described second working electrode.
In certain embodiments, in the deposition process of described step (b) and (c), using other element outside described module as described first job electrode or second working electrode to electrode.Described being used as the element of electrode can be the element that any electro-conductive material is made.Described electrolytic solution can comprise at least one in nitric acid and sulfuric acid, and the cadmium telluride in described module can incorporate in described electrolytic solution before deposition starts.Such as, described electrolytic solution can be the solution of salpeter solution or sulfuric acid and hydrogen peroxide.
In further embodiments, in step (b), using described module itself as described first job electrode to electrode.
In one embodiment, in step (b), described module be used as described first job electrode to electrode, in step (c), described module be again used as described second working electrode to electrode.Such as, in a specific embodiment, module is placed in the electrolytic solution in an electrolyzer, using its as be placed in this electrolytic solution first job electrode to electrode, make from the tellurium in module and the first element in cadmium, such as tellurium, deposits on described first job electrode.In the process of the first element deposition in described tellurium and cadmium, the second element in described tellurium and cadmium, such as cadmium concentration in the electrolytic solution can increase gradually.After the deposition of the first element in described tellurium and cadmium has carried out for some time, the current potential of described first job electrode is close to when tending to the potential value of the second element in codeposition tellurium and 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, using described module as second working electrode to electrode, make described from the tellurium in module and the second element deposition in cadmium on described second working electrode.After the deposition of the second element then in described tellurium and cadmium has carried out for some time, the current potential of described second working electrode is close to when tending to the potential value of the first element in codeposition tellurium and cadmium, again described second working electrode is replaced with first job electrode, and corresponding adjustment deposition parameter, to realize the deposition of the first element in described tellurium and cadmium.By such method, alternately tellurium and cadmium are deposited on corresponding working electrode respectively fully.
In another embodiment, deposition is carried out at least two modules in described method simultaneously reclaim tellurium and cadmium.Said method comprising the steps of: the first module is placed in the first electrolytic solution by (a), the second module is placed in the second electrolytic solution; (b) using described first module as tellurium working electrode to electrode, tellurium in described first electrolytic solution is deposited on described tellurium working electrode, using described second module as cadmium working electrode to electrode, the cadmium in described second electrolytic solution is deposited on described cadmium working electrode; C cadmium in described first electrolytic solution deposits on described cadmium working electrode by (), deposited on described tellurium working electrode by the tellurium in described second electrolytic solution.
In the process, the step making described first and second electrolyte circulation or exchanged the position of described tellurium working electrode and cadmium working electrode can be comprised further between step (b) and (c).
Exchanging of the circulation of described electrolytic solution or working electrode position can at the current potential of described tellurium working electrode close to when tending to the potential value of codeposition cadmium, or implement close to when tending to the potential value of codeposition tellurium at the current potential of described cadmium working electrode.The current potential of working electrode can contrast a reference electrode, and such as, Ag/AgCl reference electrode is monitored.In one embodiment, described in tend to codeposition cadmium potential value be the value that relative Ag/AgCl reference electrode is approximately-0.3V, described in tend to codeposition tellurium potential value be the value being approximately-0.6V relative to Ag/AgCl reference electrode.Circulation or the exchanging of working electrode position of described electrolytic solution can reach about-0.3V at the current potential of the relative Ag/AgCl reference electrode of described tellurium working electrode, or a close-0.3V but value higher than-0.3V time, or reach about-0.6V at the current potential of the relative Ag/AgCl reference electrode of described cadmium working electrode, or a close-0.6V but value lower than-0.6V time implement.In a specific embodiment, circulation or the exchanging of working electrode position of described electrolytic solution reach 0.15V to-0.3V at the current potential of the relative Ag/AgCl reference electrode of described tellurium working electrode, or more appropriately,-0.15V to-0.3V, or more appropriately,-0.15V to 0.25V, or more appropriately, a value in scope between-0.15V to 0.2V, or reach-1.0V to-0.6V at the current potential of the relative Ag/AgCl reference electrode of described cadmium working electrode, or more appropriately,-1.0V to-0.7V, or more appropriately,-1.0V to-0.8V, or more appropriately,-1.0V implements when arriving a value in the scope between-0.9V.
Described method can comprise repeating step (b) further, until deposit to fully respectively on described tellurium working electrode and cadmium working electrode from the tellurium in the first and second modules and cadmium.In one embodiment, described method comprises repeating step (b) further, until from when in the tellurium of described first and second modules or cadmium at least 95%, or preferably, till at least 99% mass percent has deposited on corresponding working electrode.In addition, described method may comprise repeating step (a) and (b) further, until tellurium in described first and second modules and cadmium fully deposit on described tellurium working electrode and cadmium working electrode respectively.When depositing to the metal level on tellurium working electrode and cadmium working electrode and being enough thick, it can be scraped off from this working electrode, to recycle, can purify to it as required before recovery.
In one embodiment, described first and second electrolytic solution are contained in the first and second electrolyzers respectively, described first and second electrolytic solution can circulate by the recycle pump connected between described first and second electrolyzers, to balance the concentration of metal ions in two electrolyzers.In another embodiment, described first and second electrolytic solution can realize circulation by a storage container, and such as, it can be realized by following steps: the electrolytic solution in one of them electrolyzer described is transferred to a storage container by (i); (ii) electrolytic solution in another electrolyzer is transferred to described in its electrolyte inside is transferred in the electrolyzer of storage container; And another electrolyzer described transferred to by the electrolytic solution in described storage container by (iii).
Described electrolytic solution can be any suitable solion, include but not limited to, the amino Propidium iodide 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, in described first and second electrolyzers, the electrolytic solution of initial handling is different electrolytic solution.In another embodiment, described first and second electrolyzer initial handlings is the same electrolytic solution that pH value is different.
Described working electrode can be applicable to for making working electrode with the material used in the electrolytic solution by any.Such as, described working electrode can include but not limited to, at least one in transparent conductive oxide (TCO) glass, platinum, graphite, copper, aluminium and iron.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 control realization respectively further and tellurium selectivity deposited to the first pH value of described tellurium working electrode and realize cadmium selectivity to deposit to the second pH value of described cadmium working electrode.In one embodiment, the described step controlling the first and second pH value respectively comprises: control the pH value in the first and second electrolyzers respectively when depositing and starting, and in deposition process, in corresponding each first and second electrolyzers, the circulation of electrolytic solution or tellurium working electrode and cadmium working electrode position exchanges, pH value in corresponding adjustment first and second electrolyzer, to ensure to remain the first pH value implementing the pH value deposited to by tellurium in the electrolyzer on tellurium working electrode, and remain the second pH value implementing the pH value deposited to by cadmium in the electrolyzer on cadmium working electrode.In one embodiment, described first pH value approximately controls in the scope of 0 to 2.0 or 9.5 to 14.0, or more appropriately, approximately controls in the scope of 12.0 to 14.0; Described second pH value approximately controls in the scope of 6.0 to 8.5, or more appropriately, approximately controls in the scope of 7.0 to 8.5.
Described method can comprise further respectively control one be suitable for selectivity deposition tellurium to the first deposition voltage on tellurium working electrode and be suitable for selectivity deposition cadmium to the second deposition voltage on cadmium working electrode.In one embodiment, the described step controlling the first and second deposition voltages respectively comprises: the deposition voltage be applied on tellurium working electrode is remained the first deposition voltage, and the deposition voltage being applied to cadmium working electrode remains the second deposition voltage.In one embodiment, described first deposition voltage is greatly in the scope of-2.5V to 0V, and described second deposition voltage is greatly in the scope of-2.5V to 0V.Described first and second deposition voltages may identical also possibility difference.
In the process, the selectivity of tellurium deposition or cadmium deposition is increased by various means.
The formation such as in certain embodiments, described module is by a kind of device comprising cadmium telluride, such as useless optoelectronic equipment.Produce by a kind of device comprising cadmium telluride the module being applicable to described method by following methods, that is: the part containing cadmium telluride of this device is exposed to the outside, or the adjacent part of the part being contained cadmium telluride is exposed to the outside, when its be positioned over deposit in electrolytic solution time, this adjacent part solubilized, in electrolytic solution, makes electrolytic solution can act on the described part containing cadmium telluride.The adjacent part of the described part containing cadmium telluride can be dissolved in electrolytic solution together with the described part containing cadmium telluride, also can prior to described being partly dissolved in electrolytic solution containing cadmium telluride.
In one embodiment, described module comprises the device of glass-base, glass protecting cap layer and the cadmium-telluride layer between this glass-base and glass protecting cap layer from one, by the glass protecting cap layer of device is removed to form described module in a certain way, described in remove mode and make described glass protecting cap layer still recyclable recycling.In one embodiment, after tellurium thereon and cadmium deposit on corresponding working electrode fully, the glass-base of described first and second modules does not have machinery, physics or infringement chemically substantially, can entirely recycling, or through certain polishing or recycling after revising operation.Described glass protecting cap layer or glass-base, or may be through polishing or revised glass protecting cap layer or glass-base, can recycle after certain mist agent or organic solution cleaning, 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 cap layer successively, heat this device make its sealing material melting layer or again its glass protecting cap layer removed after burning, just can obtain described module.In the process of deposition, described cadmium sulfide layer and cadmium-telluride layer are dissolved in electrolytic solution, and described oxidic, transparent, conductive layers and described glass-base remain unchanged substantially, after described oxidic, transparent, conductive layers being removed by methods such as polishings, the recyclable recycling of described glass-base.Described eliminate oxidic, transparent, conductive layers after glass-base can recycle with after the cleaning of aforementioned organic or inorganic solution.
For example, in the embodiment illustrated in 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 cap layer 112 successively, and wherein said glass protecting cap layer 112 is adhered on described graphite (metal) conductive layer 110 by adhesive seal material (not shown).Described adhesive seal material combustion is fallen by the described device 100 of heating by described module 150, then removes described glass protecting cap layer 112, is exposed to the outside by described conductive layer 110 and is formed.Then described module 150 is positioned in the electrolyzer 200 containing electrolytic solution, as one to electrode, described graphite (metal) conductive layer 110 on it can be dissolved in electrolytic solution together with cadmium telluride absorption layer 108 and Cadmium Sulfide transition layer 106, and the tellurium in electrolytic solution and/or cadmium are deposited on a working electrode 205 be positioned in electrolyzer 200.
As shown in Figure 2, provide a kind of system 300 comprising two electrochemical appliances in the illustrated embodiment in which, be used for reclaiming tellurium and cadmium respectively from the module comprising cadmium telluride.Described system 300 comprises the first electrochemical appliance 302 and the second electrochemical appliance 308, wherein said first electrochemical appliance 302 comprises the first electrolyzer 304 for placing electrolytic solution and is used as tellurium deposition plate and deposits the first electrode 306 on it to allow the tellurium in module, and described second electrochemical appliance 308 comprises the second electrolyzer 310 for placing electrolytic solution and is used as cadmium deposition plate and deposits the second electrode 312 on it to allow the cadmium in module.Described system 300 also comprises pH value controller 314, is used for controlling respectively realizing selectivity deposition tellurium to the first pH value of described first electrode 306 with can realize selectivity and deposit second pH value of cadmium to described second electrode 312.
First module 402 and the second module 404 are positioned over the first electrolyzer 304 and the second electrolyzer 310 respectively.Electrolytic solution in described first electrolyzer is controlled in the first pH value that is beneficial to selectivity deposition tellurium, and the electrolytic solution in described second electrolyzer is controlled in the second pH value that is beneficial to selectivity deposition cadmium.Between described first module 402 and the first electrode 306, the first voltage difference is applied by a voltage-operated device (not shown), the second voltage difference is applied, described the first electrode 306 as tellurium working electrode and the chemical reaction on the first module 402 of electrode is comprised respectively as tellurium working electrode between described second module 404 and the second electrode 312:
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 the second electrode 312 as cadmium working electrode and the chemical reaction on the second module 404 of electrode is respectively as 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 first module 402 is dissolved in the electrolytic solution in the first electrolyzer 304, tellurium is wherein 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 is wherein deposited on the second electrode 312.
In certain embodiments, reaction conditions in described each electrochemical appliance, pH value, the voltage difference etc. put on module and electrode of such as temperature, electrolytic solution suitably can regulate according to practical situation, be beneficial to cadmium telluride be dissolved down from module, tellurium and cadmium deposit to electrode and get on, and Reaction time shorten etc.
In the illustrated embodiment in which, described first electrolyzer 304 is connected with pump 318 by pipeline 316 with the second electrolyzer 310, to realize the electrolyte circulation between described first and second electrolyzers 304 and 310.When the deposition recovery of tellurium in the first electrolyzer 304 proceeds to a certain degree, when its current potential is conducive to the value of codeposition cadmium close to one, or the deposition Deng cadmium in two electrolyzers 310 reclaims and proceeds to a certain degree, when its current potential is conducive to the value of codeposition tellurium close to one, the circulation of the electrolytic solution in described first and second electrolyzers is realized, to make the homogenizing of concentration of metal ions in two electrolyzers by pump 318.In another embodiment, described system 300 may comprise a storage container, and the electrolytic solution be used in described first and second electrolyzers carries out in the process circulated, and places the electrolytic solution discharged in one of them electrolyzer temporarily.
In some other embodiment, the setting of described first electrochemical appliance 302 and the second electrochemical appliance 308 can realize the exchange of the electrode in described first electrolyzer 304 and the second electrolyzer 310, like this, when the deposition recovery of tellurium in the first electrolyzer 304 proceeds to a certain degree, when its current potential is conducive to the value of codeposition cadmium close to one, or the deposition Deng the cadmium in two electrolyzers 310 reclaims and proceeds to a certain degree, when its current potential is conducive to the value of codeposition tellurium close to one, described first electrode 306 and the second electrode 312 interchanging positions.
Described method and system provided by the present invention also can be applicable to copper-indium-galliun-selenium film solar cell.
Following instance is only provide certain guidance in order to those skilled in the art implement the claims protected invention, and therefore, these examples should not limit claims scope required for protection.
Experiment in following instance has come with other equipment of laboratory-scale.
Example one
This experiment have employed and a kind ofly combines the system comprising two electrochemical appliances that Fig. 2 is described in the preceding article to carry out the recovery of tellurium and cadmium.
This experiment have employed a CHI660D type electrochemical workstation (purchased from Chinese Shanghai Chen Hua Instrument Ltd.) and applies voltage and the reaction times of Control release.
By two laminar cadmium telluride solar panels (purchased from FirstSolar, Inc., FS-272,72.5W) 450 DEG C of heating about 10 minutes, remove its glass protecting cap layer, to be exposed to the outside by its metal conducting layer near cadmium telluride absorption layer, form the first and second cadmium telluride modules.
First platinum foil being put into described first electrolyzer and make itself and electrolyte contacts, is tellurium working electrode (tellurium deposition plate) with it; Described first cadmium telluride module is put into the first electrolyzer and makes itself and electrolyte contacts, with its be described tellurium working electrode to electrode.Second platinum foil is put into described secondth electrolyzer and make itself and electrolyte contacts, with it for cadmium electrode (cadmium deposition plate); Described second cadmium telluride module is put into the second electrolyzer and makes itself and electrolyte contacts, with its be described cadmium working electrode to electrode.
Electrolytic solution in described first electrolyzer is controlled in first pH value being suitable for tellurium selectivity being deposited on described first platinum foil, and the electrolytic solution in described second electrolyzer is controlled in second pH value being suitable for cadmium selectivity being deposited on described second platinum foil.By electrochemical workstation, first voltage difference can be applied to realize electrolysis between described first cadmium telluride module and the first platinum foil, make to be deposited on described first platinum foil from the tellurium on described first cadmium telluride module; And between described second cadmium telluride module and the second platinum foil, apply second voltage difference to realize electrolysis, make to be deposited on described second platinum foil from the cadmium on described second cadmium telluride module.
When the current potential of tellurium working electrode (the first platinum foil) tends to the value of codeposition cadmium close to one, or when the current potential of cadmium working electrode (the second platinum foil) tends to the value of codeposition tellurium close to one, the position of described first platinum foil and the second platinum foil is exchanged, be transferred to the second electrolyzer by the first platinum foil, the second platinum foil is transferred to the first electrolyzer.
Then the pH value in the first electrolyzer is adjusted to the second pH value, the pH value in the second electrolyzer is adjusted to the first pH value.Between described first cadmium telluride module and the second platinum foil, apply the second voltage difference, make to be deposited on described second platinum foil from the cadmium on described first cadmium telluride module; And the first voltage difference is applied between described second cadmium telluride module and the first platinum foil, make to be deposited on described first platinum foil from the tellurium on described second cadmium telluride module.
Repeatedly can repeat the position exchanging the first and second platinum foils when the described current potential at tellurium working electrode (the first platinum foil) tends to the value of codeposition tellurium close to the current potential of a value or cadmium working electrode (the second platinum foil) tending to codeposition cadmium close to, and the step of the value of corresponding adjustment/control ph and voltage difference, until tellurium on described first and second cadmium telluride modules and cadmium deposit on described first and second platinum foils respectively fully.
After electrolytic deposition completes, utilizing energy spectrometer and/or Inductive Coupled Plasma Emission Spectrometer ICP to analyze being deposited on the material that described first and second platinum foils deposit, recording the mass percent of cadmium on the mass percent of tellurium on the first platinum foil and the second platinum foil.
In described first and second electrolyzers, all use sodium sulfate (analyze flow 0.2M, purchased from traditional Chinese medicines group chemical reagent Shanghai company limited) to carry out series of experiments for electrolytic solution.Wherein, the pH value sulfuric acid of electrolytic solution or sodium hydroxide regulate, and can increase the temperature of electrolytic solution with silicone oil bath, make it higher than room temperature.
Parameter in described series of experiments, comprises the pH value putting on the voltage difference of electrode, the temperature of electrolytic solution and electrolytic solution as shown in table 1 below.Described experiment has used complete for about 5 hours.In each experiment obtained 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 shows.
Table 1
As shown in table 1, the first pH value deposited when applicable tellurium is less than 2.1 or be greater than 9, when second pH value of applicable cadmium deposition is between 6.0 to 8.5, tellurium deposition plate and cadmium deposition plate obtain highly purified tellurium (such as respectively, up to 100wt%) and highly purified cadmium (such as, up to 96.5wt%).
Example two
Being positioned in electrolytic solution by a cadmium telluride module makes cadmium telluride wherein be dissolved in this electrolytic solution, setting comprises electrolyte ph, put on the deposition parameter of the voltage (or sedimentation potential) of electrode and the temperature of electrolytic solution, the first element (tellurium or cadmium) in described electrolytic solution in tellurium and cadmium is deposited on first working electrode.After the deposition of the first element in described tellurium and cadmium carries out for some time, described first working electrode is replaced to the second working electrode, and corresponding adjustment deposition parameter, the second element (cadmium or tellurium) making to state in electrolytic solution in tellurium and cadmium deposits on described second working electrode.
Reference electrode, the first and second working electrodes are respectively with the first and second platinum electrodes, with the 3rd platinum electrode be the first or second working electrode to electrode, control the sedimentation potential between working electrode and reference electrode, and surveying work electrode and to the deposition current between electrode.Be electrolytic solution with salpeter solution, make cadmium telluride with Cd
2+and HTeO
2+form be dissolved in wherein.The pH value of described salpeter solution is improved or reduces by interpolation nitric acid or sodium hydroxide.
Implement two groups of experiments by first the tellurium in salpeter solution being deposited to the first working electrode and then the cadmium in salpeter solution being deposited to the second working electrode, its experiment parameter is as shown in table 2 below.In each experiment obtained 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 shows.
Table 2
Implement two groups of experiments by first the cadmium in salpeter solution being deposited to the second working electrode and then the tellurium in salpeter solution being deposited to the first working electrode, its experiment parameter is as shown in table 3 below.In each experiment obtained 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 shows.
Table 3
As shown in tables 2 and 3, by alternately tellurium and cadmium being deposited to respectively the method on the first and second working electrodes under suitable pH value and sedimentation potential, highly purified tellurium and cadmium can be obtained, such as, when pH value is 0 and current potential is suitable, can deposits and obtain highly purified tellurium, then pH value is transferred to about 8.5, under a suitable current potential, highly purified cadmium can be obtained again.
Although be described in detail Partial Feature of the present invention and described in a specific embodiment, under the prerequisite not departing from spirit of the present invention, various change and replacement can be carried out to the present invention.Same, those skilled in the art also can obtain disclosed by the invention other according to normal experiment and change and equivalent.All these change, and replace and within the design of claim that equivalent all defines in the present invention and scope.
Claims (24)
1. be used for comprising from one or more the method reclaiming tellurium and cadmium the module of cadmium telluride respectively, the method comprises:
A module is placed in electrolytic solution by ();
(b) by the tellurium in electrolytic solution and the first element deposition in cadmium on first job electrode; And
(c) by the tellurium in electrolytic solution and the second element deposition in cadmium on second working electrode;
Wherein using described module as described first job electrode in the deposition process of described step (b) to electrode.
2. a method of claim 1, comprises the step regulating the pH value of electrolytic solution, be applied at least one parameter in the temperature of voltage on electrode and electrolytic solution further between described step (b) and (c).
3. the method for claim 1, comprises repeating step (b) and (c), further until have the tellurium of at least 95% mass percent or cadmium to deposit on described working electrode.
4. the method for claim 1, using other element outside described module as described second working electrode in described step (c) to electrode.
5. method as claimed in claim 4, wherein said electrolytic solution comprises at least one in nitric acid and sulfuric acid, and the cadmium telluride in described module dissolves in described electrolytic solution before the deposition.
6. the method for claim 1, using described module as described second working electrode in the deposition process of described step (c) to electrode.
7. the method for claim 1, wherein said module comprises glass-base and cadmium-telluride layer, and the depositional mode of described tellurium and cadmium makes described glass-base can recycled in its entirety.
8. method as claimed in claim 7, wherein said module is from a device, described device comprises glass-base, transparent conductive oxide layer, cadmium sulfide layer, cadmium-telluride layer, sealing material layer and glass protecting cap layer successively, wherein said module be the described device of heating by its sealing material melting layer or burning, then glass protecting cap layer removed rear formation.
9. method as claimed in claim 8, it comprises:
In described deposition process by described cadmium sulfide layer and cadmium-telluride layer molten in electrolytic solution, and keep described glass-base and transparent conductive oxide layer substantially constant;
After described deposition completes, described transparent conductive oxide layer is removed from described glass-base; And
Reclaim described glass-base.
10. the method for claim 1, wherein described step (a) comprising: the first module is placed in the first electrolytic solution, and the second module is placed in the second electrolytic solution; Described step (b) comprising: using described first module as tellurium working electrode to electrode, tellurium in described first electrolytic solution is deposited on described tellurium working electrode, using described second module as cadmium working electrode to electrode, the cadmium in described second electrolytic solution is deposited on described cadmium working electrode; Described step (c) comprising: deposited to by the cadmium in described first electrolytic solution on described cadmium working electrode, is deposited on described tellurium working electrode by the tellurium in described second electrolytic solution.
11. methods as claimed in claim 10, comprise the step making described first and second electrolyte circulation or described tellurium working electrode and cadmium working electrode are exchanged further between described step (b) and (c).
12. methods as claimed in claim 11, during a value between the scope that the current potential of the relative Ag/AgCl reference electrode of described tellurium working electrode reaches 0.15V to-0.3V, or the step making electrolyte circulation or working electrode is exchanged described in carrying out during a value between the scope that the current potential of the relative Ag/AgCl reference electrode of described cadmium working electrode reaches-1.0V extremely-0.6V.
13. methods as claimed in claim 11, comprise repeating said steps (b) to (c) further, until have at least the tellurium of 95% mass percent or cadmium to deposit on working electrode.
14. methods as claimed in claim 13, comprise repeating step (a) to (c) further.
15. methods as claimed in claim 11, wherein said first and second electrolytic solution are placed in two electrolyzers respectively, described in make the step of electrolyte circulation be realize by being connected to circulation pump between described two electrolyzers.
16. methods as claimed in claim 11, wherein said first and second electrolytic solution are placed in two electrolyzers respectively, described in the step of electrolyte circulation is comprised: the electrolytic solution in one of them electrolyzer is moved on to a storage container by (i); (ii) electrolytic solution in another electrolyzer is moved on to described in its electrolyte inside is moved on in the electrolyzer of storage container; And the electrolytic solution in described storage container is moved on to another electrolyzer described by (iii).
17. methods as claimed in claim 11, comprise taking a step forward of described step (c): the step making the first and second electrolyte circulation described in correspondence or tellurium working electrode and cadmium working electrode are exchanged, the pH value of corresponding adjustment electrolytic solution, be applied to working electrode and the step at least one parameter in the temperature of the voltage on electrode, electrolytic solution thereof.
18. the method for claim 1, the first pH value wherein for making tellurium deposit on tellurium working electrode is controlled in the scope between 0 to 2.0 or between 9.0 to 14.0, and is controlled in the scope between 6.0 to 8.5 for the second pH value making cadmium deposit on cadmium working electrode.
19. methods as claimed in claim 18, wherein said first pH value is controlled in the scope between 12.0 to 14.0, and described second pH value is controlled in the scope between 7.0 to 8.5.
20. 1 kinds of systems reclaiming tellurium and cadmium from the module comprising cadmium telluride respectively, this system comprises:
First electrochemical appliance, it comprises the first electrolyzer for placing electrolytic solution and is used as tellurium deposition plate with the first electrode making the tellurium in module deposited thereon;
Second electrochemical appliance, it comprises the second electrolyzer for placing electrolytic solution and is used as cadmium deposition plate with the second electrode making the cadmium in module deposited thereon; And
PH value controller, is used for controlling respectively realizing selectivity deposition tellurium to the first pH value of described first electrode with can realize selectivity and deposit second pH value of cadmium to described second electrode;
Wherein, described first and second electrochemical appliances at least can make the position that is negotiable or the first and second electrodes of the electrolytic solution in described first and second electrolyzers to exchange.
21. systems as claimed in claim 20, wherein said first and second electrolyzers are connected with pump by pipeline, when being mounted with electrolytic solution in described first and second electrolyzers, described pipeline and pump make the electrolytic solution in described first and second electrolyzers can realize regular or irregular circulation.
22. systems as claimed in claim 20, comprise storage container further, carry out being used in the process of electrolyte circulation placing the electrolytic solution of releasing from one of them electrolyzer between described first and second electrolyzers.
23. systems as claimed in claim 20, comprise voltage-operated device further, are used for the first voltage controlling respectively can realize being deposited to by tellurium on described first electrode and second voltage that cadmium can be realized to deposit to described second electrode.
24. systems as claimed in claim 20, comprise monitoring device further, are used for monitoring the concentration of tellurium at least one in described first and second electrolyzers or cadmium.
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| CN105862059A (en) * | 2016-05-12 | 2016-08-17 | 中南大学 | Method for recovering tellurium through cyclone electrolysis of solution containing tellurium |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5997718A (en) * | 1997-05-12 | 1999-12-07 | Drinkard Metalox, Inc. | Recycling of CdTe photovoltaic waste |
| US6391165B1 (en) * | 1997-05-13 | 2002-05-21 | First Solar, Llc | Reclaiming metallic material from an article comprising a non-metallic friable substrate |
| CN101125678A (en) * | 2007-08-31 | 2008-02-20 | 侯仁义 | Reclaiming device for cadmium telluride and reclaiming method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5997718A (en) * | 1997-05-12 | 1999-12-07 | Drinkard Metalox, Inc. | Recycling of CdTe photovoltaic waste |
| US6391165B1 (en) * | 1997-05-13 | 2002-05-21 | First Solar, Llc | Reclaiming metallic material from an article comprising a non-metallic friable substrate |
| CN101125678A (en) * | 2007-08-31 | 2008-02-20 | 侯仁义 | Reclaiming device for cadmium telluride and reclaiming method thereof |
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