NZ535454A - An electrochemical apparatus incorporating an electrode for the reduction of polysulfide species - Google Patents

An electrochemical apparatus incorporating an electrode for the reduction of polysulfide species

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Publication number
NZ535454A
NZ535454A NZ535454A NZ53545403A NZ535454A NZ 535454 A NZ535454 A NZ 535454A NZ 535454 A NZ535454 A NZ 535454A NZ 53545403 A NZ53545403 A NZ 53545403A NZ 535454 A NZ535454 A NZ 535454A
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NZ
New Zealand
Prior art keywords
electrode
negative
electrochemical apparatus
cobalt
positive
Prior art date
Application number
NZ535454A
Inventor
Stephen Fletcher
Dijk Nicholas Joseph Van
Original Assignee
Regenesys Tech Ltd
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Filing date
Publication date
Application filed by Regenesys Tech Ltd filed Critical Regenesys Tech Ltd
Publication of NZ535454A publication Critical patent/NZ535454A/en

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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8694—Bipolar electrodes
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inert Electrodes (AREA)
  • Catalysts (AREA)
  • Hybrid Cells (AREA)

Abstract

Disclosed is an electrochemical apparatus which comprises a single cell or an array of cells, each cell with a positive chamber containing a positive electrode and an electrolyte solution and a negative chamber containing a negative electrode and an electrolyte solution containing sulfide, wherein: the redox couple of the positive chamber differs from the redox couple of the negative chamber; the positive and negative chambers are separated from one another by a cation exchange membrane; and the negative electrode is an electrode which incorporates therein a polysulfide species reduction catalyst, which catalyst comprises at least one organic complex of a transition metal.

Description

535454 - i - AN ELECTROCHEMICAL APPARATUS INCORPORATING AN ELECTRODE FOR THE REDUCTION OF POLY SULFIDE SPECIES The present invention relates to an electrochemical 5 apparatus in which the negative electrode incorporates a catalyst for lowering the reduction overpotential of polysulfide species and, in particular, to an electrode which incorporates a catalyst for the sulfide/ polysulfide redox reduction reaction, which catalyst comprises at least ^10 one organic complex of a transition metal.
This reaction is described, for example, in US-A-^ 4485154. Typical cells in which this reduction reaction is carried out are known as regenerative fuel cells in which the chemical fuels are regenerated by reversing the current 15 flow.
To maximise the energy efficiency of regenerative fuel cells it is necessary to perform the oxidation and reduction reactions of the fuels as closely as possible to their electrochemical reversible potentials. Any inefficiencies 20 manifest as additional potentials called overpotentials. Not ^ surprisingly, it is an object of much research in fuel cells to minimise overpotentials. One way to minimize ^ overpotentials is by incorporating catalysts in the electrode materials.
In carrying out the sulfide/polysulfide redox reduction reaction the current density at an electrode carrying out this reaction is limited by the combined effects of restricted mass transport and slow electrochemical reaction kinetics. Many authors (Lessner, P.M., McLaron, F.R., 30 Winnick, J. and Cairns, E.J., J. Appl. Electrochem., 22 (1996) 927-934, Idem., ibid. 133 (1986) 2517) have utilized a high surface area electrode (e.g. an expanded metal mesh) i intellectual propertv office i of n.z. -9 AUG 2006 to overcome these effects by providing a high interfacial area per unit volume. The same authors have utilized Ni, Co or Mo metals, or the sulfides of these metals, to catalyse the electrode reaction. However, metal sulfides have a tendency to dissolve.
In WO 00/44058 the use of an electron mediator ("electrocatalyst") is described which is included in suspension in the solution in the negative chamber for the sulfide/polysulfide reaction, the mediator having a particle size of up to 1 micrometre in diameter and preferably comprising copper, nickel, iron, cobalt or molybdenum, or a salt of copper, nickel, iron, cobalt or molybdenum.
Typically the salt is a sulfide.
Although the use of a colloidal mediator enhances the observed current, the mediator particles circulate freely in the negative chamber and may have a detrimental effect upon other components of the cell.
In the present invention we have developed a means of decreasing the overpotential of the sulfide/polysulfide redox reaction by immobilizing one or more complexes of metal ions in or on the electrode material which then remain substantially undissolved.
Accordingly, the present invention provides an electrochemical apparatus which comprises a single cell or an array of cells, each cell with a positive chamber containing a positive electrode and an electrolyte solution and a negative chamber containing a negative electrode and an electrolyte solution containing sulfide, wherein: the redox couple of the positive chamber differs from the redox couple of the negative chamber, the positive and negative chambers are separated from one another by a cation exchange membrane, and intellectual property office of n.z. - 9 AUG 2006 the negative electrode is an electrode which incorporates therein a polysulfide species reduction catalyst, which catalyst comprises at least one organic complex of a transition metal.
These organic complexes of transition metals may be adsorbed on electrode surfaces by evaporation of various non-aqueous solutions, or may be deposited by precipitation, or may be deposited by vapour deposition, or may be incorporated directly as solids. The electrodes may be made of metal, activated carbon, or any other form of carbon, or any other conducting material.
Preferred transition metal complexes for use in the present invention are those of manganese, iron, cobalt, nickel or copper, the organic complexes of cobalt being particularly preferred.
Suitable organic complexes are those formed with phthalocyanine, bis(salicylaldehyde), bis(salicylidene)-1,2-phenyldiamine, bis(salicylidene)-ethylenediamine, bis (salicylideiminato-3-propyl)-methylamine and 5,10,15,20-tetraphenyl-21H,23H-porphine.
Particularly preferred catalysts are the organic complexes of cobalt and in particular cobalt (II) phthalocyanine, cobalt (II) bis(salicylaldehyde), or a mixture thereof.
The sulfide/polysulfide redox reduction reaction takes place in the negative chamber of an electrochemical cell during energy storage. The sulfide contained in the solution in the negative chamber may be one or more of sodium, potassium, lithium or ammonium sulfide and may preferably be present in a concentration of from 1 to 2M. The electrochemical cell is completed by adding a different intellectual PROPERTY office of n.l - 9 AUG 2006 RFrch/cn redox couple to the positive chamber. For example, this maybe the bromine/bromide couple.
The different redox couples circulate independently and are kept apart by a membrane permeable to monovalent cations, typically made of Nafion™. The latter is a commercially available perfluorosulfonate membrane material manufactured by E I Dupont de Nemours & Co. (Wilmington, DE). Nafion™ membranes have acceptable ionic conductivity, and good long-term mechanical and chemical stability. They are manufactured with thicknesses in the range 25-183 |nm, and have specific conductances of approximately 0.01 S/cm in concentrated sodium polysulfide solutions at 25°C, provided divalent cations are excluded from the electrolyte solution. Structurally, Nafion™ is a co-polymer comprising backbone units of hydrophobic tetrafluoroethylene, and side chains of perfluorinated vinyl ether terminated by hydrophilic sulfonate groups. Membranes from other companies can also be used provided their structures permit the transport of cations ions rapidly and selectively from one side of the cell to the other. Examples are Aciplex™ (Asahi Chemical Industry Co. Ltd/Japan) and Flemion™ (Asahi Glass Co. Ltd/Japan), The equilibrium cell voltage is about 1.5 V when the bromine/bromide redox couple is placed in the positive chamber of the electrochemical cell. This forms a so-called "regenerative fuel cell". During discharge, and depending upon electrode surface area, the voltage of each regenerative fuel cell may fall to 1.3 V. During recharge, and depending upon electrode surface area, the voltage of each regenerative fuel cell may rise to 1.9 V. A significant fraction of this latter voltage is traceable to the slow speed of reduction of various polysulfide species. The intellectual property office of n.z. -9 AUG 2006 RPrciwcn present invention provides a means of speeding up the reduction of these polysulfide species, and thus provides a means of decreasing the overpotential of recharge. Since the energy losses of fuel cells (which appear as heat) are directly proportional to the overpotentials of charge and recharge, decreasing the overpotential of recharge results in a significant cost saving.
The present invention will be further described with reference to the accompany drawings, in which: Figure 1 illustrates the sulfur stoichiometry for sodium polysulfide species; Figure 2 illustrates a voltammogram in an Na2S3.4 solution where S42- is the predominant species (Example 5); Figure 3 illustrates a voltammogram in a Na2S,j.6 solution where S52- is the predominant species (Example 6); and Figure 4 illustrates the effect of catalyst concentration on voltammograms in an Na2S4.6 solution where S52" is the predominant species (Example 7).
Referring to Figure 1, it is well known to those skilled in the art that different polysulfide species dominate in different concentration ranges of total dissolved sulfur. The general formula of the sodium polysulfide solutions used in the present work is Na2Sn, where 1 < n < 5, and we refer to n as the sulfur stoichiometry. As shown in Figure 1, below a sulfur stoichiometry of 4.45 the predominant reducible ion is S42-, whereas above a sulfur stoichiometry of 4.45 the predominant reducible ion is S52-. Above a sulfur stoichiometry of approximately 4.8 colloidal sulfur is unavoidably present, which prevents the preparation of pure Ss2- solutions. intellectual property office of n.2. -9 AUG 2006 received WO 03/083967 PCT/GB03/01316 The present invention will be further described with reference to the following Examples. In these Examples the term "ink" is used to mean a fine suspension of particles in an evaporable solvent which is suitable for printing.
EXAMPLE 1 In this example the construction of a working electrode containing cobalt(II) phthalocyanine in a 2% w/w catalyst-10 to-carbon loading is described.
To 51.2 mg of finely ground cobalt(II) phthalocyanine, there were added 2 drops of isophorone, which were mixed to form a viscous slurry. To this was added 6.4 g of 15 proprietary carbon ink (Ercon Inc, West Wareham, MA) that contained 40% by weight carbon. After thorough mixing, the resulting paste was screen-printed onto a polyester support, through a stainless steel screen with a mesh count of 80 strands per centimetre, to create the working electrode. 20 After oven drying the working electrode at 120°C for one hour, a layer of proprietary insulator (Ercon Inc, West Wareham, MA) was screen printed over the carbon, through a stainless steel screen with a mesh count of 112 strands per centimetre, to decrease the electrode size to a 3mm diameter 25 disk. The insulator was then cured at 120°C for one hour.
EXAMPLE 2 ■30 In this example the construction of a working electrode containing Cobalt(II) Phthalocyanine in a 4% w/w catalyst-to-carbon loading is described.
To 102.9 mg of finely ground cobalt (II) phthalocyanine, there were added 2 drops of isophorone, which were mixed to form a viscous slurry. To this was added 6.4 g of proprietary carbon ink (Ercon Inc, West Wareham, MA) that 5 contained 40% by weight carbon. After thorough mixing, the resulting paste was screen-printed onto a polyester support, through a stainless steel screen with a mesh count of 80 strands per centimetre, to create the working electrode. After oven drying the working electrode at 120°C for one 10 hour, a layer of proprietary insulator (Ercon Inc, West Wareham, MA) was screen printed over the carbon, through a stainless steel screen with a mesh count of 112 strands per centimetre, to decrease the electrode size to a 3mm diameter disk. The insulator was then cured at 120°C for one hour.
EXAMPLE 3 Electrodes containing 8% and 16% w/w catalyst-to-carbon loading were prepared according to the method of Example 2 20 by increasing the amounts of cobalt(II) phthalocyanine.
EXAMPLE 4 (Control) A control electrode containing no catalyst was also 25 constructed. To 6.0g of proprietary carbon ink (Ercon Inc, West Wareham, MA) were added 2 drops of isophorone, to form a consistent paste. After thorough mixing, this was screen printed onto an inert polyester support, through a stainless steel screen with a mesh count of 80 strands per centimetre, 30 to create the working electrode. After oven drying the working electrode at 120°C for one hour, a layer of proprietary insulator (Ercon Inc, West Wareham, MA) was screen printed over the carbon, through a stainless steel screen with a mesh count of 112 strands per centimetre, to decrease the electrode size to a 3mm diameter disk. The insulator was then cured at 120°C for one hour.
EXAMPLE 5 This example describes the testing procedure for catalysts for the reduction of S42".
The screen-printed working electrode as described in Example 2 was placed in a cell containing 100 mL of solution, in such a way that--the disk electrode was fully immersed. The solution, consisting of 1 M Na2S3.4 and 1 M NaBr in water, was thermostatted at 25°C. The electrode was voltammetrically cycled at 10 mV s_1, with the first ten voltammograms being recorded. Figure 2 illustrates the effectiveness of various catalysts (third cycle shown).
For each catalyst eight replicate electrodes were prepared and tested. Overpotentials were measured at -0.160 mA (corresponding to 2.25 mA cm-2) and are listed in Table 1. It is evident that various different compounds of transition metals exert catalytic effects on the reduction of S«2". - 9 -TABLE 1 Compilation of overpotentials (± 10 mV) for different catalysts at 4% loading, in Na2S3.4 solutions, where S42" is the predominant ion. The lowest overpotentials indicate the best catalysts. Median values, eight replicates.
Overpotential/mV @ Catalyst 2.25 mA cm"2 Cobalt (II) Bis(salicylaldehyde) -144 Cobalt (II) Sulfide -298 Iron(II) Phthalocyanine -350 Bis(salicylidene)-1,2- phenylenediamino-Cobalt(II) -393 Bis(salicylidene)- ethylenediamino-Gobalt(II) -480 Vitamin B12 (cyanocobalarain) -552 Cobalt (II) Phthalocyanine -571 5,10,15,20-tetraphenyl-21H,23H- porphine Cobalt(II) -606 Bis(salicylideniminato-3- propyl)-methylamino-Cobalt(II) -780 Manganese(II) Phthalocyanine -813 Nickel(II) Phthalocyanine -813 Copper(II) Phthalocyanine -813 No Catalyst -813 - 10 -EXAMPLE 6 This example describes the testing procedure for catalysts for the reduction of S52-.
The screen-printed working electrode as described in Example 2 was placed in a cell containing 100 mL of solution, in such a way that the disk-shaped working electrode was fully immersed. The solution, consisting of 1 M Na2S4.6 and 1 M NaBr in water, was thermostatted at 25°C. The electrode was voltammetrically cycled at 10 mV s-1, with the first ten voltammograms being recorded. Figure 3 illustrates the effectiveness of various catalysts (third cycle shown).
For each catalyst eight replicate electrodes were prepared and tested. Overpotentials were measured at -0.160 mA (corresponding to 2.25 mA cm-2) and are listed in Table 2. It is evident that various different compounds of transition metals exert catalytic effects on the reduction of S52-.
TABLE 2 Compilation of overpotentials (+10 mV) for different catalysts at 4% loading, in Na2S4.6 solution, where S52" is the predominant ion. The lowest overpotentials indicate the best catalysts. Median values, eight replicates.
Overpotential/mV @ Catalyst 2.25 mA cm Cobalt(II) Phthalocyanine -194 Manganese(II) Phthalocyanine -237 Cobalt(II) Bis(Salicylaldehyde) -246 Iron(II) Phthalocyanine -357 Cobalt(II) Sulfide -378 Bis (salicylidene)-1,2- phenylenediamino-Cobalt(II) -393 Vitamin B12 (cyanocobalamin) -400 5,10,15,20-tetraphenyl- 21H,23H-porphine Cobalt(II) -530 Bis(salicylidene)- ethylenediamino-Cobalt(II) -559 Copper(II) Phthalocyanine -703 Nickel(II) Phthalocyanine -714 Bis(salicylideniminato-3-propyl)-methylamino- Cobalt(II) -715 No Catalyst -835 EXAMPLE 7 -2 In this example the effect of catalyst loading is 25 described.
The screen printed working electrodes as described in Examples 1 to-4 were tested one at a time by being placed in a cell containing 100 mL of solution such that the disk-shaped working electrode was fully immersed. The solution, consisting of 1 M Na2S4.6 and 1 M NaBr in water, was thermostatted at 25°C.
Figure 4 illustrates the effect of using different cobalt phthalocyanine catalyst concentrations in the carbon 5 electrodes (third cycle shown). The electrode was voltammetrically cycled at 10 mV s"1, with the first ten voltammograms being recorded. For each measurement eight replicate electrodes were prepared and tested. It is evident that the maximum catalytic effect is achieved at about 8% 10 loading by weight.

Claims (8)

- 13 - What is claimed is:
1. An electrochemical apparatus which comprises a single cell or an array of cells, each cell with a positive chamber containing a positive electrode and an electrolyte solution and a negative chamber containing a negative electrode and an electrolyte solution containing sulfide, wherein: the redox couple of the positive chamber differs from the redox couple of the negative chamber, the positive and negative chambers are separated from one another by a cation exchange membrane, and the negative electrode is an electrode which incorporates therein a polysulfide species reduction catalyst, which catalyst comprises at least one organic complex of a transition metal.
2. An electrochemical apparatus as claimed in claim 1 which is an energy storage and/or power delivery apparatus.
3. An electrochemical apparatus as claimed in claim 1 or claim 2 wherein the catalyst is an organic complex of manganese, iron, cobalt, nickel or copper.
4. An electrochemical apparatus as claimed in claim 3 wherein the organic complex is a complex of cobalt.
5. An electrochemical apparatus as claimed in any one of the preceding claims wherein the catalyst comprises cobalt (II) phthalocyanine, cobalt (II)bis(salicylaldehyde) or a mixture thereof. intellectual property office of n.z. -9 AUG 2006 received - 14 -
6. An electrochemical apparatus as claimed in any one of the preceding claims wherein the negative electrode is the negative surface of a bipolar electrode.
7. An electrochemical apparatus as claimed in claim 1, substantially as herein described with reference to any one of the Examples and/or Figures.
8. An electrochemical apparatus as claimed in any one of claims 1 to 6, substantially as herein described. intellectual property office of n.2. -9 AUG 2006 received
NZ535454A 2002-03-27 2003-03-26 An electrochemical apparatus incorporating an electrode for the reduction of polysulfide species NZ535454A (en)

Applications Claiming Priority (2)

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GBGB0207214.8A GB0207214D0 (en) 2002-03-27 2002-03-27 A catalyst for lowering the reduction overpotential of polysulfide species
PCT/GB2003/001316 WO2003083967A2 (en) 2002-03-27 2003-03-26 An electrode for the reduction of polysulfide species

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EP (1) EP1488470A2 (en)
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KR (1) KR20040101369A (en)
CN (1) CN1312802C (en)
AU (1) AU2003212543A1 (en)
CA (1) CA2480089A1 (en)
GB (1) GB0207214D0 (en)
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NO (1) NO20044521L (en)
NZ (1) NZ535454A (en)
TW (1) TWI230481B (en)
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Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4958133B2 (en) * 2004-09-15 2012-06-20 独立行政法人産業技術総合研究所 Electrode catalyst for hydrogen electrode of low temperature fuel cell
JP2006202686A (en) * 2005-01-24 2006-08-03 Asahi Kasei Corp Metal compound fuel cell electrode catalyst
GB0505087D0 (en) * 2005-03-12 2005-04-20 Acal Energy Ltd Fuel cells
IN266777B (en) 2006-03-24 2015-06-01 Acal Energy Ltd
GB0608079D0 (en) 2006-04-25 2006-05-31 Acal Energy Ltd Fuel cells
GB0614338D0 (en) 2006-07-19 2006-08-30 Acal Energy Ltd Fuel cells
GB0614337D0 (en) 2006-07-19 2006-08-30 Acal Energy Ltd Fuel Cells
GB0718349D0 (en) 2007-09-20 2007-10-31 Acal Energy Ltd Fuel cells
GB0718577D0 (en) 2007-09-24 2007-10-31 Acal Energy Ltd Fuel cells
GB0801198D0 (en) 2008-01-23 2008-02-27 Acal Energy Ltd Fuel cells
GB0801199D0 (en) 2008-01-23 2008-02-27 Acal Energy Ltd Fuel cells
WO2012048276A2 (en) 2010-10-08 2012-04-12 Caridianbct, Inc. Customizable methods and systems of growing and harvesting cells in a hollow fiber bioreactor system
WO2015073913A1 (en) 2013-11-16 2015-05-21 Terumo Bct, Inc. Expanding cells in a bioreactor
WO2015148704A1 (en) 2014-03-25 2015-10-01 Terumo Bct, Inc. Passive replacement of media
EP3198006B1 (en) 2014-09-26 2021-03-24 Terumo BCT, Inc. Scheduled feed
WO2017004592A1 (en) 2015-07-02 2017-01-05 Terumo Bct, Inc. Cell growth with mechanical stimuli
US11965175B2 (en) 2016-05-25 2024-04-23 Terumo Bct, Inc. Cell expansion
US11685883B2 (en) 2016-06-07 2023-06-27 Terumo Bct, Inc. Methods and systems for coating a cell growth surface
US11104874B2 (en) 2016-06-07 2021-08-31 Terumo Bct, Inc. Coating a bioreactor
CN117247899A (en) 2017-03-31 2023-12-19 泰尔茂比司特公司 cell expansion
US11624046B2 (en) 2017-03-31 2023-04-11 Terumo Bct, Inc. Cell expansion
US12234441B2 (en) 2017-03-31 2025-02-25 Terumo Bct, Inc. Cell expansion
EP4314244B1 (en) 2021-03-23 2025-07-23 Terumo BCT, Inc. Cell capture and expansion
US12209689B2 (en) 2022-02-28 2025-01-28 Terumo Kabushiki Kaisha Multiple-tube pinch valve assembly
USD1099116S1 (en) 2022-09-01 2025-10-21 Terumo Bct, Inc. Display screen or portion thereof with a graphical user interface for displaying cell culture process steps and measurements of an associated bioreactor device
CN121260818B (en) * 2025-12-04 2026-02-13 山东海化集团有限公司 Preparation method of modified zinc-bromine flow battery carbon felt negative electrode and carbon felt negative electrode prepared by method

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2125590C3 (en) * 1971-05-24 1981-02-19 Robert Bosch Gmbh, 7000 Stuttgart ten anthraquinone cyanine
US4252875A (en) * 1980-04-14 1981-02-24 Honeywell Inc. Electro-catalysts for the cathode(s) to enhance its activity to reduce SoCl2 in Li/SoCl2 battery
US4485154A (en) * 1981-09-08 1984-11-27 Institute Of Gas Technology Electrically rechargeable anionically active reduction-oxidation electrical storage-supply system
US4405693A (en) * 1981-10-05 1983-09-20 Honeywell Inc. High rate metal-sulfuryl chloride batteries
US4710437A (en) * 1984-09-19 1987-12-01 Honeywell Inc. High rate metal oxyhalide cells
GB2337150B (en) * 1998-05-07 2000-09-27 Nat Power Plc Carbon based electrodes
GB9820109D0 (en) * 1998-09-15 1998-11-11 Nat Power Plc Vitrified carbon compositions
GB2346006B (en) * 1999-01-20 2001-01-31 Nat Power Plc Method of carrying out electrochemical reactions

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NO20044521L (en) 2004-11-04
ZA200407663B (en) 2006-06-28
AU2003212543A1 (en) 2003-10-13
WO2003083967A3 (en) 2004-10-28
MY141844A (en) 2010-07-16
US20050112447A1 (en) 2005-05-26
GB0207214D0 (en) 2002-05-08
TW200306683A (en) 2003-11-16
EP1488470A2 (en) 2004-12-22
WO2003083967A2 (en) 2003-10-09
CN1643723A (en) 2005-07-20
CA2480089A1 (en) 2003-10-09
JP2005527942A (en) 2005-09-15
CN1312802C (en) 2007-04-25
TWI230481B (en) 2005-04-01

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