CN103153869A - Wall for separating electrolytes for the selective transfer of cations through the wall, and associated manufacturing method and transfer method - Google Patents
Wall for separating electrolytes for the selective transfer of cations through the wall, and associated manufacturing method and transfer method Download PDFInfo
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- CN103153869A CN103153869A CN2011800361485A CN201180036148A CN103153869A CN 103153869 A CN103153869 A CN 103153869A CN 2011800361485 A CN2011800361485 A CN 2011800361485A CN 201180036148 A CN201180036148 A CN 201180036148A CN 103153869 A CN103153869 A CN 103153869A
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- wall
- electrolytic solution
- active coating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
- H01M50/437—Glass
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a wall for separating electrolytes, comprising an active layer (22) made of a material capable of developing intercalation and deintercalation reactions for the selective transfer of cations through the wall, and a supporting layer (21) which is made of a porous material and used as carrier for the active layer (22). A method for selectively transferring cations uses such a transfer wall (2). According to a method for manufacturing such a transfer wall (2), a solution including an active material in the form of a powder, a binder, and a solvent is prepared, and then the surface of a supporting layer (21) made of a porous material is coated with said solution and the solvent is evaporated.
Description
Technical field
The present invention relates to a kind of for transmitting the manufacture method of cationic electrolytic solution separates walls, described wall by the wall selectivity and transmitting cationic method by described wall selectivity.The invention still further relates to and a kind ofly guarantee that by the wall that is fit to positively charged ion is sent to the electrolysis-type method of the second electrolyte solution from the first electrolyte solution of the ion of the identical charges that contains one or more types or different electric charges.
Background technology
Known such method is as separates walls, the wall that a kind of chalcogenide by containing molybdenum bunch (molybdenum cluster) forms, the Mo that is called Xie Fuer phase (Chevrel phase) that particularly describes in International Patent Application WO 2009/007598
6X
8Phase.The method is also the theme of following publication:
-Electrochemical?reactions?of?reversible?intercalation?in?Chevrel?compounds?for?cationic?transfer-Principle?and?application?on?Co
2+ion;S.Seghir,C.Boulanger,S.Diliberto,J.M.Lecuire,M.Potel,O.Merdrignac-Conanec;dans?Electrochemistry?Communications,10,2008,1505-1508.
-Selective?transfer?of?cations?between?two?electrolytes?using?the?intercalation?properties?of?Chevrel?phases;S.Seghir,C.Boulanger,S.Diliberto,M.Potel,J-M.Lecuire;dans?Electrochimica?Acta,55,2010,1097-1106.
These document descriptions can be by by containing the formula Mo that is called the Xie Fuer phase
6X
8The wall that the material of (wherein, X=S, Se, Te) is made transports positively charged ion, Xie Fuer mutually in, the reversible redox system of following type occurs:
X is the numerical value that typically changes between 0 to 4.
These systems are according to positively charged ion M
n+, chalcogen X and this ternary compound (ternary) stoichiometric number x character and change.
In the experimental installation that uses the selectivity transfer approach, transmit wall and comprising respectively the titanium electrode that scribbles platinum that serves as anode and serving as between two compartments of stainless steel electrode of negative electrode.The first compartment comprises various cationic the first electrolytic solution that contains pending effluent liquid.The second compartment contains accepts selected cationic the second electrolytic solution.
Set up galvanic current between anode and negative electrode.In the whole electrochemistry operation of the group of two compartments, cationic embedding (intercalation) occurs in M
xMo
6S
8(for example, pending effluent liquid is different from positively charged ion M each other to the/the first electrolyte interface
n+, M'
n+, M "
n+Mixture) locate, according to:
This identical positively charged ion M
n+Take off embedding (deintercalation) inversely at M
xMo
6S
8The/the second electrolyte interface (for example, M
n+Increment solution (valorisation solution)) locate to carry out, according to:
Therefore, Xie Fuer mutually in the movability of metallic cation make desolvation (disolvated) positively charged ion M
n+Can be in the situation that do not transmit any other chemical substance from a kind of medium transfer to another kind of from one or other compartments.
The composition powder mixture that is suitable for required materials chemistry stoichiometric number by thermal sintering obtains dish type transmission wall.Therefore, having obtained thickness is the active material disk of 2 to 5 millimeters.
Test by the wall of selenium and sulphur phase composite is shown, and particularly the positively charged ion of following metal can be sent to another kind from a kind of electrolytic solution: iron, manganese, cobalt, nickel, chromium, copper, zinc, cadmium.The current density restrictions that obtains is 10 to 20A/m
2, the induced current productive rate is higher than 90%, or even higher than 98%, and selectivity is fine.
Also demonstration of this test, along with the thickness reduction of wall, the restriction of transfer rate increases.Yet, the required strong mechanical constraints of wall the reduction of its thickness.
In addition, cannot obtain lithium with these walls transmits.Yet, lithium in industry, the especially increase in demand in the electric car battery.
Summary of the invention
Goal of the invention
Therefore, the purpose of this invention is to provide and allow good transfer rate and have to transmit the selectivity that cationic expansion selects and transmit wall.
The invention scheme
Be conceived to these targets, theme of the present invention is the electrolytic solution separates walls, it comprises for transmit positively charged ion by the wall selectivity and embeds and take off the sealing active coating that the material of embedding reaction is made by producing, and it is characterized in that it comprises the carrier layer (support layer) that the porous material by the carrier that serves as active coating forms.
The inventor successfully prepares has the wall that porous support that physical strength is provided and its thickness can low-down active coatings.They have found that porous support does not hinder the electrochemical reaction that occurs on the active coating level.By reducing the thickness of active coating, the transfer rate that reaches far surpasses the ratio limit according to prior art, and this is one of purpose of the present invention.
Porous material is selected from, for example, and mullite, silicon-dioxide, glass fibre, quartz or ceramic.These materials provide the effect that realizes wall required character, that is, and and physical strength, for the patience that is included in product in electrolytic solution and porousness.
The porosity of porous material is, for example, and 0.4 to 0.6.This value representation material is with respect to the ratio of volume.It comprises the good tradeoff between the physical strength of the volume that is present in the electrolytic solution in porous support and described carrier.
Especially, the material of active coating is to serve as master network (host network) and have the binary or the ternary material that hold character (cation reversible accommodation properties) reversible according to the positively charged ion of redox reaction.The inventor finds that Xie Fuer can produce to embed/take off unique material that embedding reacts to form selectivity transmission wall, but, in general, the master network of stablizing and redox reaction occuring.
The material of active coating is, for example, and metal chalcogenide (metallic chalcogenide).
Especially, the metal chalcogenide is the chalcogenide (Mo with molybdenum bunch (molybdenum cluster)
nX
n+2Or M
xMo
nX
n+2), X is selected from S(sulphur), Se(selenium) and the Te(tellurium) chalcogen, M is metal.Numerical value n is selected from, for example, and 1,1.5,2,3,4,5,6 and 9.
According to another kind of composition, the material of active coating is the lithium of combination of oxide form, phosphoric acid salt or fluorochemical or these forms and the compound of metal, and metal is selected from nickel, cobalt, iron, manganese, vanadium, titanium and chromium.Can find out that these materials can produce embedding and take off the embedding reaction, and can selectivity transmit positively charged ion, especially lithium.
According to the manufacture method that transmits wall, preparation comprises the solution of active material, binding agent and the solvent of powder type, then applies the surface of the carrier layer that is made of porous materials with described solution, and evaporating solvent is to form the sealing active coating on carrier layer.
The active coating that can find out acquisition seals, and it guarantees that they do not mix when wall separates electrolytic solution.And although be initially powder formulation, active coating conducts electricity, and it shows that particle contacts with each other and makes redox reaction to produce on the whole surface-area of active coating.The layer that obtains is very thin, and is consistent with the purpose that begins to determine.
Binding agent is for example, to gather (vinylidene).
Solvent is, for example, and 1-Methyl-2-Pyrrolidone.
When 80% ratio of the material weight of powder type exists (do not comprise and desolventizing), result is satisfactory.
The material of powder type has, for example, and the granularity of 30 to 100 μ m.
According to improvement, solution also comprises the graphite of powder type except other materials.This makes active coating can have electroconductibility.
According to improvement, (polishing, polish) active coating is until show carrier layer by active coating in polishing.Therefore, this has reduced the thickness of active coating.Although should reduce, kept sealing, do not affect the productive rate of wall.The current density limit value being detected increases.
Theme of the present invention is also the selectivity positively charged ion extraction method that transmits by electrochemistry, be characterised in that it is used as the electrolytic solution separates walls with above-mentioned transmission wall and passes through on the one hand, the first electrolytic solution and on the other hand, produce potential difference between the second electrolytic solution or described transmission wall to cause cationic embedding in the transmission wall of the first electrolytic solution side, cationic diffusion in described wall, then in the second electrolytic solution they take off embedding, guarantee cationic transmission by described transmission wall.
According to other characteristics:
At least a in-electrolytic solution is non-water.Electrolytic solution between compartment can be different, the difference of background salt (background salts) character particularly, their acidic levels, the existence of coordination agent (complexant), solvent is the character of inorganic or organic non-aqueous solvent particularly, as, for example, DMSO, DMF, ionic liquid, solid electrolyte, etc.
-transmit wall to be electrically connected to the device of measuring electromotive force between the described wall that lays respectively in each electrolytic solution and reference electrode, and the potential regulating that applies between described electrolytic solution is to suitable (adjusted to suit).
-at the first electrolytic solution with transmit between wall and produce potential difference, and to take off embedding at the positively charged ion of the second electrolytic solution side be that chemistry by the chemical oxidizing agent in the second electrolytic solution takes off embedding.
-guarantee that by electrolytic solution in the middle of being arranged on continuously transmission wall between the electrolytic solution of end and one or more between various transmission wall a series of (continuous, a succession of) positively charged ion transmits.
-metal electrodeposition through transmitting is on negative electrode.
-at least two kinds of transmission wall of different nature compartments that the first compartment is in parallel with each separate, and are used for the different positively charged ions that selectivity transmits the embedding electrolytic solution that respectively transmits particular adjustments on wall that connects.Be sent to the compartment that separates and make it possible to specific each metal that reclaims simultaneously, for example, for the source solution that contains lithium and cobalt ion, use by Mo
6S
8The active coating of making is used for transmitting cobalt, by LiMn
2O
4The second layer selectivity of making transmits lithium.
Description of drawings
Reading following the description, namely afterwards will understand better the present invention with reference to the description that accompanying drawing is made, and other characteristics and advantages of the present invention will become clear, wherein:
Fig. 1 is the sectional view according to transmission wall of the present invention;
Fig. 2 is for the X-ray diffraction analysis figure of making according to the porous material of the wall of Fig. 1;
Fig. 3 and Fig. 4 are the porousness of wall of check Fig. 1 or the schematic diagram of seal test device;
Fig. 5 is the schematic diagram of device;
Fig. 6 shows the several compartments that use series connection and the setting that transmits wall;
Fig. 7 shows the setting of using several compartments in parallel and transmitting wall.
Embodiment
Transmit wall 2 according to dish type of the present invention and formed by porous support 21, the accurate active coating 22 of deposition on porous support 21.In the fs, by preparation porous support 21, in subordinate phase, by active coating 22 is applied to carrier 21, carry out the preparation of sealing pad.
The preparation of porous support
Scheme is as follows: the first, mix the material that is formed by the following of 5g:
The kaolin of-2.52g (hydrated aluminium silicate) Al
2Si
2O
5(OH)
4,
The aluminium oxide Al of-3.80g
2O
3,
The stock yam starch of-1g.
Make the powdered mixture homogenizing in porcelain mortar, then with the acetone humidifying of minimum volume to prevent from forming reunite (aggregate).With natural ventilation (in free air) drying composite 14h.Then the part powder 10 minutes of the approximately 1g that obtains of hand-ground again in mortar, by under the pressure of 2 tonnes in the mould of 25mm diameter compacting made it form disk in 5 minutes.The disk that compresses is that 1mm is thick.Make sample stand twice continuous heat treatment operation.
Make the yam starch can oxidation in air to the first heat operation of 300 ° of C.Remove organic binder bond in 1 hour, thereby produce porousness.Gratifying physical strength is guaranteed in the other processing of 8 to 24 hours under 1100 ° of C.After current thermal treatment, having obtained diameter is that 24mm and thickness are two kinds of disks of 1mm.Surface-area is 4.5cm
2
Carried out X-ray diffraction analysis (Fig. 2) on porous disc.The spectrogram of record shows not to be had impurity and to form alumina phase and mullite mutually.
Use pH test paper and nitric acid HNO
3, with the porosity of the mode test assessment disk that illustrates on the figure of Fig. 3: the change of pH test paper color has confirmed the suitable porosity of disk.Porosity detects to have provided for 10% initial yam starch content and is by volume 0.553 and be 0.501 mean value for 5% content.
The preparation of active coating
The subordinate phase of preparation disk comprises that the physics of the one side of porous support 21 applies.In the illustrated embodiment, be used in Xie Fuer phase suspension (formula Mo in volatile solvent
6X
8, wherein X is chalcogen) apply.By the powder compound Mo that comprises active material
6S
8Or Mo
6Se
8The preparation work electrode.Poly-(vinylidene) that adds also referred to as PVDF, plays binding agent.
Synthetic by pottery, by Mo+2MoSe
2Mixture, homogenize and under the pressure of 250MPa cold reduction to cylinder (cylinders), under argon partial pressure, carry out in the sealing molybdenum crucible in electric arc furnace, then heat 50h under 1300 ° of C, obtain Mo
6Se
8Phase.Identical grinding 50 μ m Screening Treatments also are applied to this compound.
Check their purity by the X-ray diffractogram of the synthetic powder that obtains on diffractometer.
Dependence contain intermediate metal as, for example, Cu
3Mo
6S
8Ternary compound carry out mutually being combined to based on the Xie Fuer of sulphur.In sealed silica envelope, in a vacuum and the synthetic 50h that carries out this ternary compound under 1000 ° of C.Original mixture is by homogenizing in ball mill 30 minutes and Cu, the MoS of cold reduction under the pressure of 250MPa
2, and the micropowder (micrometric powder) of Mo form.
Flow down and make molybdenum powder deoxidation 3h at hydrogen under 1000 ° of C, prepare MoS by in sealed silica envelope, the stoichiometric mixture of element being heated to 800 ° of C of as many as gradually
2Powder.
The granularity of the powdered product of using is in the scope of 30 to 100 microns.
Synthetic by pottery, by Mo+2MoSe
2Mixture, homogenize and under the pressure of 250MPa cold reduction to cylinder, under argon partial pressure, carry out in the sealing molybdenum crucible in electric arc furnace, then heat 50h under 1300 ° of C, obtain Mo
6Se
8Phase.Check their purity by the X-ray diffractogram of the reaction product that obtains on diffractometer.
By applying, active coating is applied to porous support
Xie Fuer phase matrix (matrix) situation
Form the suspension that the PVDF by the Xie Fuer phase of 95% powder type and 5% forms in 1-Methyl-2-Pyrrolidone (hereinafter referred to as NMP), the solid Mo of 0.1g
6X
8The PVDF of phase, 0.005g is dispersed in the NMP of 1ml.Stirred whole 2 hours.
Use the pasteur pipette, with several Mo
6X
8NMP-PVDF suspension is placed on the porous support disc surfaces to cover as far as possible equably whole surface-area.Then, integral body is placed in baking oven 1h to remove nmp solvent.Under these conditions, the Mo that obtains
6S
8Or Mo
6Se
8Film to be attached to thickness be the about disc surfaces of 80 μ m.And, according to the seal test of Fig. 4, the pH test paper do not have variable color facts sustain the suitable obstruction in hole of porous disc.Conductive test has proved good electrically contacting between particle.
Also used the paint-on technique of spin coating principle.They have provided the coating identical with before structure.
For Mo
6S
8Synthesizing of two yuan of phases, carry out the copper chemistry by the electrochemical method after applying coating and take off embedding.
Li
xM
yO
zType matrix of oxide situation
According to another embodiment, with satisfying general formula Li
xM
yO
zActive material as matrix composition wall, wherein, y and z are integers, for example, include, without being limited to Li
xCoO
2, LiMn
2O
4, LiV
3O
8, LiNiO
2Or LiMnO
2Active material also can comprise the mixture of metal M.Preparation principle remains and passes through Li
xM
yO
zSuspension applies porous support.
During coating solution by Li
xM
yO
zPulverulent mixture preparation, it comprises by weight 80% active material, 10% the PVDF that plays the binding agent effect and 10% the carbon of guaranteeing electroconductibility.Mixture is fully homogenized in mortar.
With the powdered mixture of 0.2 gram in the NMP of 1ml, stirring under 2 hours prepare suspension in 1-Methyl-2-Pyrrolidone.
Use the pasteur pipette, with the Li of several
xM
yO
zNMP-PVDF solution is placed on the porous support disc surfaces, to cover as far as possible equably whole surface-area.This operation also can use spin coating technique to carry out.Then, integral body is placed in baking oven 1h to remove nmp solvent.Under these conditions, the oxide film that obtains is attached to disc surfaces, and thickness is about 80 μ m.And seal test has confirmed the suitable obstruction in the hole of porous disc.Conductive test has proved the good electrical properties of film.
No matter the type of matrix must use equadag coating 23 to electrically contact to meet (follow) phase boundary potential in the disk perimeter setting.Spread upon the periphery of disk with this coating, overlap on the face of active coating 22.
The selectivity transfer approach
Illustrating on Fig. 5 used the device of implementing the selectivity transfer approach according to transmission wall of the present invention.This device comprises and contains two compartments 11 that are suitable for holding electrolytic solution and separated by separates walls 13 and 12 groove 1, is provided with the transmission wall 2 that is comprised of disk 2 in separates walls 13, is arranged in wall 13 with sealing means.
This device also comprises the anode A 1 that is arranged in the first compartment 11 and the negative electrode C2 that is arranged in the second compartment 12.Can apply potential difference Δ E to apply and to check current i between electrolytic solution E1 and E2 between anode A 1 and negative electrode C2 by known method itself.
Typically, below this device is used as:
Set up whole intensity (intensiostatic) state of deciding between anode A 1 and negative electrode C2.Let us is called RH, the RH of the material of master network, active coating 22.In the whole electrochemistry operation of two compartments, pending original solution electrolytic solution E1 comprises the cationic mixture of different metal and identical or different electric charge, for example, and M
n+, M'
n+, M "
n'
+, electrolytic solution E2 is the increment solution of metal M, and following reaction occurs:
-at the at the interface embedding positively charged ion Mn+ of active coating 22 with electrolytic solution E1, as follows:
-at active coating 22 and electrolytic solution E2(for example, the increment solution of Mn+) take off at the interface this identical positively charged ion of embedding, it is counter movement, and is as follows:
Therefore, the movability of metallic cation makes desolvation positively charged ion M in master network
n+Can be in the situation that do not transmit any other chemical substance from a kind of medium transfer to another kind of from one or other compartments.
As point out, in a general way, be arranged in two compartments 11 that comprise anode A 1 and negative electrode C2,12 electrolytic solution, can be different, the character of background salt particularly, acidic levels, the existence of coordination agent, solvent is the character of organic or inorganic non-aqueous solvent (DMSO, DMF, ionic liquid, solid electrolyte, etc.) particularly.Therefore, for example, ion can be sent to from sulfate medium in chloride media and the described medium of indiffusion.
In the modification of Fig. 6, groove comprises three compartments.Two end compartment 11', 12' are equivalent to the compartment 11 and 12 of the embodiment shown in Fig. 1.Contain the other compartment 15 of electrolytic solution E3 between two compartment 11' and 12', and by separates walls 13', 13 " ' separating with these compartments, separates walls 13', 13 " comprises that respectively one or more are according to transmission wall 2' of the present invention, 2 ".These transmit wall 2', 2 " can be same nature, to improve simply the selectivity that is sent to compartment 12' from compartment 11'.They can be also of different nature, can bases, and for example, carry out the specific inspection of the electromotive force that applies between the various compartments of different cation separation and differently control.For example, the positively charged ion of two types can be sent to compartment 15 from compartment 11', only a kind ofly is sent to compartment 12' from compartment 15.Therefore, disk can be used for carrying out various required separating and processing with the various combinations that pass a parameter.
In the situation that the modification of Fig. 6, middle electrolytic solution or electrolytic solution E3 also can be identical or different with one or both electrolytic solution E1 or E2.
In the another kind of modification that shows in Fig. 7, groove comprises three compartments.Central strip chamber 11 " the first compartment 11 that is equivalent to the embodiment shown in Fig. 2.LH compartment 12 " the second compartment 12 that is equivalent to the embodiment shown in Fig. 2.The other compartment 16 that contains electrolytic solution E3 is positioned at the right side of the first compartment, and by comprising that one or more are according to transmission wall 2 of the present invention " ' separates walls 13 " ' separate.According to separates walls 13,13 " ', these transmit wall 2 " ' be of different nature, transmit the certain cationic of each compartment with selectivity.For example, the first electrolytic solution E1 is the source solution that contains cobalt and lithium ion.Between the first and second compartments 11 ", 12 " first transmit wall 2 to have by Mo
6S
8The active material of making is used for selectivity and transmits cobalt, and the first and the 3rd compartment 11 ", second between 16 transmit wall 2 " ', have LiMn
2O
4The active material of making, being used for simultaneously, selectivity transmits lithium.The first compartment 11 " comprises anode A 1 ", produces the transmission electric current between described anode A 1 " and the negative electrode C2 in the second compartment ", and described anode A 1, and " and the another kind between the negative electrode C3 in the 3rd compartment 16 transmits electric current.
The porous disc 21 that is covered by the active coating 22 based on sulphur Xie Fuer phase is used as according to the transmission wall 2 in the device of Fig. 5, as previously described.For respectively based on Mo
6S
8And Mo
6Se
8And the disk of two types under different current densities, studied and contained the first electrolytic solution E1(at the Na of medium 0.1M
2SO
4, 0.1M H
2SO
4In the M of 0.1M
2+Cationic solution) the first compartment 11 and contain the Na that the second increment electrolytic solution E2(contains 0.1M
2SO
4H with 0.1M
2SO
4) the second compartment 12 between cationic transmission.The purpose of this research is to detect different positively charged ion M
n+Transmission induced current productive rate (faradaic yield), to measure the Mo of porous
6S
8And Mo
6Se
8The restricted condition of disk and assessment current density restrictions.Transport process is based on before condition, namely in a large number by being used for M
X/2Mo
6X
8The Mo of stoichiometry deposition
6X
8The cationic amount of embedding of assessment.Table 1 and 2 shows active material and is respectively Mo
6S
8And Mo
6Se
8The result that obtains.
Table 1
Table 2
Can find out that the induced current productive rate is noticeable, because they are higher than 90%, and current density far surpasses those (about 16A/m of prior art
2).
For the sulphur phase, at low current density (3.2A/m
2) under 2.10-2mol/h/m
2Extremely at high current density (70A/m
2) under 3mol/h/m
2Speed under set up quantitative transmission.For be evaluated as the Mo of 80 μ m in conjunction with thickness
6S
8, it seems that the value of back be limiting speed.Consider and contain active material Mo
6Se
8Disk, only for positively charged ion Cd
2+, Zn
2+, Mn
2+, Cu
2+, and In
3+, the transfer rate of these selenium in mutually is identical with the order of magnitude of sulphur phase, i.e. 3.2A/m
2Under 510
-2Mol/h/m
2And 70A/m
2Under 4mol/h/m.It is 70A/m that table 3 and 4 has provided for each element current density
2Under transfer rate.
Table 3
Table 4
Selectivity
In the cation selective transport process, only contain in the first electrolytic solution E1 of cationic mixture one type and transmit by wall.Selectivity is caused by the following fact: during electrolysis procedure, be applied to voltage between two faces of active coating 22 and make it possible to embed and take off the only positively charged ion of a type of embedding.In order to transmit other positively charged ions, must apply higher electromotive force, it is not the purpose of present method.The positively charged ion of the type through transmitting has minimum embedding electromotive force and the maximum embedding electromotive force that takes off, to represent with respect to the reference potential that is provided by saturated calomel electrode (SCE).
Cationic synthetic mixture is transmitted experiment, as: Co/Ni, Cd/Zn, Cd/Ni, Zn/Mn, Cd/Co, Co/Fe, Ni/Fe and Cd/Co/Ni.
In the following examples of being undertaken by two kinds of equimolar cation mixts (0.1M), transmit selectivity with positively charged ion Mn
+The transmission selection ratio represent, be expressed as and consider all substances M in compartment 2
it n+The positively charged ion that transmits add and, the positively charged ion M that material transmits
t n+The M of amount
t n+/ ∑ M
it n+Ratio, for example, for Co
2++ Ni
2+Mixture, Co
t/ (Co
t+ Ni
t).
Therefore, along with selectivity improves, this ratio is near 100%, if do not produce selectivity, value is 50%.
Table 5 and 6 has provided the optional ratio who obtains for various mixtures under different current densities.The value that provides for different current densities is corresponding to the average selectivity ratio that obtains under each hour during the electrolysis of 1 to 7 hour.
Table 5
Table 6
Can find out that the optional ratio depends on current density.For high current density, selectivity is higher, thereby causes high transfer rate.The character of the active coating 22 of wall plays an important role in cationic selectivity transmits.Use seleno matter, at Ni
2+Under existence, Cd
2+Or Zn
2+The transmission selectivity really be increased to as many as 99%.Cd in the Cd/Co mixture
2+Situation under identical discovery can be arranged.Selectivity is the impact of the low thickness of receptor 1 activity layer 22 not.
In this embodiment, active coating 22 is by material LiCoO
2Make, thickness is about 80 μ m.This material is used for, for example, and in the positive electrode of lithium ion battery.The first electrolytic solution is the Na at 1M
2SO
4The aqueous solution of the 1M of Li+ in medium.The second electrolytic solution that serves as the solution that rises in value is Na
2SO
4The aqueous solution of 1M.Provided result in table 7.
Table 7
| Current density (A/m 2） | 4 | 8 | 12 | 16 | 32 | 41 |
| Transmit induced current productive rate (%) | 98 | 99 | 98 | 99 | 99 | 41 |
| Transfer rate (mol/h/m 2） | 0.14 | 0.2 | 0.41 | 0.6 | 1.21 | 0.82 |
This embodiment is similar to embodiment 2, except the second electrolytic solution that serves as the solution that rises in value is propylene carbonate solvent and tetrabutylammonium perchlorate's solution.Anode is to be made by the titanium that scribbles platinum, and negative electrode is made by stainless steel.Provided result in table 8.
Table 8
Embodiment 4
From by depositing Mo at the porous disc according to such scheme
6S
8On the film that-PVDF produces, by the excess material of manual polishing except striping, be 2400 SiC disk several seconds until the color of porous support manifests by the friction granularity.Therefore, the part of transmission material only remains in the hole.With the mode identical with experiment before carry out and test this operate in approximately 80A/m applicatory
2Current density under more favourable transport property is provided significantly, higher than before, and do not affect the induced current productive rate.
Embodiment 5: from mixed Li
2SO
4And CoSO
4Transmit Li in electrolytic solution
+
In this embodiment, active coating is by material LiMn
2O
4Make, thickness is about 80 μ m.The first electrolytic solution is to contain positively charged ion Li in sulfate medium
+(1M) and Co
2+Aqueous solution (0.5M).The second electrolytic solution that serves as the solution that rises in value is that concentration is the Na of 1M
2SO
4Solution.Provided result in table 9.
Table 9
Claims (19)
1. electrolytic solution separates walls, comprise and to produce the sealing active coating (22) that embeds and take off the material of embedding reaction, be used for transmitting positively charged ion by described wall selectivity, it is characterized in that, described wall comprises the carrier layer (21) that the porous material by the carrier that serves as described active coating (22) forms.
2. wall according to claim 1, wherein, described porous material (21) is selected from mullite, silicon-dioxide, glass fibre, quartz or ceramic.
3. wall according to claim 1, wherein, the porosity of described porous material (21) is included between 0.4 to 0.6.
4. wall according to claim 1, wherein, the material of described active coating (22) is to serve as master network and have the binary or the ternary material that hold character reversible according to the positively charged ion of redox reaction.
5. wall according to claim 4, wherein, the material of described active coating (22) is the metal chalcogenide.
6. wall according to claim 5, wherein, described metal chalcogenide is the chalcogenide (Mo that contains molybdenum bunch
nX
n+2Or M
xMo
nX
n+2).
7. wall according to claim 4, wherein, the material of described active coating (22) is the lithium of combination of oxide compound, phosphoric acid salt or fluorochemical form or these forms and the compound of metal, described metal is selected from nickel, cobalt, iron, manganese, vanadium, titanium and chromium.
8. the preparation method of the described wall of any one in a claim 1 to 7, according to the method, preparation comprises the solution of active material, binding agent and the solvent of powder type, then apply the surface of the carrier layer (21) of porous material with described solution, evaporate described solvent to be formed on the sealing active coating (22) on described carrier layer (21).
9. method according to claim 8, wherein, described binding agent is poly-(vinylidene).
10. method according to claim 8, wherein, described solvent is 1-Methyl-2-Pyrrolidone.
11. method according to claim 8, wherein, the material of described powder type exists with 80% ratio of the weight outside desolventizing.
12. method according to claim 8, wherein, the material of described powder type has the granularity of 30 to 100 μ m.
13. method according to claim 8, wherein, described solution also comprises the graphite of powder type except other materials.
14. method according to claim 8 wherein, is polished described active coating (22) until described carrier layer (21) manifests by described active coating (22).
15. cation selective extracting method that transmits by electrochemistry, it is characterized in that, to be used as the electrolytic solution separates walls by the described transmission wall of any one (2) according to claim 1 to 7, undertaken by following, on the one hand, the first electrolytic solution (E1) and, on the other hand, produce potential difference (Δ E) between the second electrolytic solution (E2) or described transmission wall (2), guarantee described cationic transmission by described transmission wall (2), to cause in cationic embedding described in the described transmission wall (2) of described the first electrolytic solution side, in cationic diffusion described in described wall, then in described the second electrolytic solution (E2) they take off embedding.
16. method according to claim 15, wherein, at least a in described electrolytic solution (E1, E2) is non-water.
17. method according to claim 15, wherein, described transmission wall (2) is electrically connected to the device of measuring electromotive force between the described wall lay respectively in each electrolytic solution (E1, E2) and reference electrode (33,34), and with the described potential regulating that applies between described electrolytic solution (E1, E2) to suitable.
18. method according to claim 15, wherein, produce potential difference (Δ E) between described the first electrolytic solution (E1) and described transmission wall (2), and to take off embedding at the described positively charged ion of described the second electrolytic solution (E2) side be that chemistry by the chemical oxidizing agent in described the second electrolytic solution takes off embedding.
19. method according to claim 1 wherein, guarantees that by transmission wall (2) and one or more the middle electrolytic solution (E3) between various described transmission wall of being arranged on continuously between end electrolytic solution (E1, E2) a series of positively charged ions transmit.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1056066A FR2963026B1 (en) | 2010-07-23 | 2010-07-23 | ELECTROLYTE SEPARATION WALL FOR SELECTIVE CATION TRANSFER THROUGH THE WALL, MANUFACTURING METHOD, AND TRANSFER METHOD. |
| FR1056066 | 2010-07-23 | ||
| PCT/FR2011/051602 WO2012010766A1 (en) | 2010-07-23 | 2011-07-06 | Wall for separating electrolytes for the selective transfer of cations through the wall, and associated manufacturing method and transfer method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103153869A true CN103153869A (en) | 2013-06-12 |
Family
ID=43428618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800361485A Pending CN103153869A (en) | 2010-07-23 | 2011-07-06 | Wall for separating electrolytes for the selective transfer of cations through the wall, and associated manufacturing method and transfer method |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20130126354A1 (en) |
| EP (1) | EP2595922A1 (en) |
| JP (1) | JP2013539404A (en) |
| CN (1) | CN103153869A (en) |
| AU (1) | AU2011281483A1 (en) |
| CA (1) | CA2805998A1 (en) |
| CL (1) | CL2013000160A1 (en) |
| FR (1) | FR2963026B1 (en) |
| WO (1) | WO2012010766A1 (en) |
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|---|---|---|---|---|
| FR3002527A1 (en) * | 2013-02-26 | 2014-08-29 | Univ Lorraine | ELECTROLYTE SEPARATION WALL FOR SELECTIVE CATION TRANSFER THROUGH THE WALL AND PROCESS FOR PRODUCING SAID WALL |
| US10695725B2 (en) | 2016-03-03 | 2020-06-30 | Enlighten Innovations Inc. | Intercalation membrane |
| WO2020254912A1 (en) * | 2019-06-17 | 2020-12-24 | 3M Innovative Properties Company | Membrane assemblies |
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|---|---|---|---|---|
| CN1106615A (en) * | 1993-03-26 | 1995-08-09 | 罗纳·布朗克化学公司 | Method for the preparation of a microporous diaphragm |
| CN1259773A (en) * | 1999-08-14 | 2000-07-12 | 惠州Tcl金能电池有限公司 | Compound polymer dielectric membrane and lithium batttery made by using said membrane |
| FR2918079A1 (en) * | 2007-06-27 | 2009-01-02 | Univ Paul Verlaine | METHOD AND A DEVICE FOR SELECTIVE EXTRACTION OF CATIONS BY ELECTROCHEMICAL TRANSFER IN SOLUTION AND APPLICATIONS OF THIS PROCESS. |
| CN100502097C (en) * | 2004-07-07 | 2009-06-17 | 株式会社Lg化学 | New organic/inorganic composite porous film and electrochemical device prepared thereby |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11312415A (en) * | 1998-04-28 | 1999-11-09 | Kyocera Corp | Solid electrolyte |
| EP1359636A1 (en) * | 2001-09-03 | 2003-11-05 | Matsushita Electric Industrial Co., Ltd. | Method for manufacturing electrochemical device |
| JP3702234B2 (en) * | 2002-02-25 | 2005-10-05 | 西日本環境エネルギー株式会社 | Sodium solution electrolyzer and sodium recovery system using the same |
| JP5076134B2 (en) * | 2004-06-08 | 2012-11-21 | 国立大学法人東京工業大学 | Lithium battery element |
| PL1782489T3 (en) * | 2004-07-07 | 2021-05-31 | Lg Chem, Ltd. | Organic/inorganic composite porous separator and electrochemical device comprasing the same. |
| JP2007335206A (en) * | 2006-06-14 | 2007-12-27 | Nissan Motor Co Ltd | Bipolar battery |
| JP5281896B2 (en) * | 2006-11-14 | 2013-09-04 | 日本碍子株式会社 | Solid electrolyte structure for all solid state battery, all solid state battery, and manufacturing method thereof |
| WO2008124047A1 (en) * | 2007-04-03 | 2008-10-16 | Ceramatec, Inc. | Electrochemical process to recycle aqueous alkali chemicals using ceramic ion conducting solid membranes |
| JP2008285388A (en) * | 2007-05-21 | 2008-11-27 | Toyota Motor Corp | Lithium ion conductivity improving material |
-
2010
- 2010-07-23 FR FR1056066A patent/FR2963026B1/en not_active Expired - Fee Related
-
2011
- 2011-07-06 AU AU2011281483A patent/AU2011281483A1/en not_active Abandoned
- 2011-07-06 CN CN2011800361485A patent/CN103153869A/en active Pending
- 2011-07-06 WO PCT/FR2011/051602 patent/WO2012010766A1/en active Application Filing
- 2011-07-06 JP JP2013520178A patent/JP2013539404A/en active Pending
- 2011-07-06 EP EP11743300.3A patent/EP2595922A1/en not_active Withdrawn
- 2011-07-06 CA CA2805998A patent/CA2805998A1/en not_active Abandoned
- 2011-07-06 US US13/811,434 patent/US20130126354A1/en not_active Abandoned
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2013
- 2013-01-16 CL CL2013000160A patent/CL2013000160A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106615A (en) * | 1993-03-26 | 1995-08-09 | 罗纳·布朗克化学公司 | Method for the preparation of a microporous diaphragm |
| CN1259773A (en) * | 1999-08-14 | 2000-07-12 | 惠州Tcl金能电池有限公司 | Compound polymer dielectric membrane and lithium batttery made by using said membrane |
| CN100502097C (en) * | 2004-07-07 | 2009-06-17 | 株式会社Lg化学 | New organic/inorganic composite porous film and electrochemical device prepared thereby |
| FR2918079A1 (en) * | 2007-06-27 | 2009-01-02 | Univ Paul Verlaine | METHOD AND A DEVICE FOR SELECTIVE EXTRACTION OF CATIONS BY ELECTROCHEMICAL TRANSFER IN SOLUTION AND APPLICATIONS OF THIS PROCESS. |
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| US20130126354A1 (en) | 2013-05-23 |
| JP2013539404A (en) | 2013-10-24 |
| AU2011281483A1 (en) | 2013-02-07 |
| FR2963026B1 (en) | 2013-03-15 |
| CA2805998A1 (en) | 2012-01-26 |
| FR2963026A1 (en) | 2012-01-27 |
| WO2012010766A1 (en) | 2012-01-26 |
| EP2595922A1 (en) | 2013-05-29 |
| CL2013000160A1 (en) | 2013-08-23 |
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