EP2433324A1 - Galvanic element having a mercury-free negative electrode - Google Patents
Galvanic element having a mercury-free negative electrodeInfo
- Publication number
- EP2433324A1 EP2433324A1 EP10721708A EP10721708A EP2433324A1 EP 2433324 A1 EP2433324 A1 EP 2433324A1 EP 10721708 A EP10721708 A EP 10721708A EP 10721708 A EP10721708 A EP 10721708A EP 2433324 A1 EP2433324 A1 EP 2433324A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- conductive agent
- negative electrode
- galvanic element
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000006258 conductive agent Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 229910052755 nonmetal Inorganic materials 0.000 abstract 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0433—Molding
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/12—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with flat electrodes
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
Definitions
- the present invention relates to a galvanic element, which is characterized in particular by a mercury-free negative electrode. Furthermore, the present invention relates to a method with which such galvanic elements can be produced with mercury-free negative electrode.
- Galvanic elements such as batteries and accumulators are used today in many areas. They serve in particular to supply portable devices with electrical energy. In very small devices such as watches and hearing aids, the galvanic elements are preferably used in the form of button cells. Especially hearing aids have a relatively high power consumption. Therefore, hearing aids are usually supplied with batteries of the electrochemical system zinc-air, which are characterized by a particularly high capacity. Commercially available zinc-air batteries are not rechargeable and must be disposed of after use. However, this is problematic because they can contain up to about 1% by weight of mercury which should not be released into the environment.
- mercury in electrodes such as in the anodes of zinc-air and silver oxide batteries has the function of improving the electrical contact between the individual zinc particles. It thus increases the internal overall conductivity of the electrodes. This is particularly important in the case of advanced unloading condition.
- the conductive active material zinc is namely converted during the discharge to non-conductive zinc oxide, so that the power line within the electrode to resist ever greater resistance. Without sufficient As a rule, due to poor electrical contact within an electrode, not all zinc particles are converted into zinc oxide. The theoretical energy content of an electrode is not fully exploited accordingly.
- the object of the present invention was to provide such galvanic elements.
- the focus should be on the development of electrodes, which are optimized in view of the mentioned problem of incomplete reaction of zinc and in this respect at least not significantly lag behind electrodes containing mercury.
- a galvanic element according to the invention comprises a mercury-free negative electrode, which is distinguished in particular by the fact that it essentially consists only of a metal or a metal alloy and a non-metallic conductive agent.
- a mercury-free negative electrode which is distinguished in particular by the fact that it essentially consists only of a metal or a metal alloy and a non-metallic conductive agent.
- the negative electrode of a galvanic element according to the invention consists essentially of particles of the metal or the metal alloy, whose surface is at least partially coated with the non-metallic conductive agent.
- these individual particles are additionally in electrical contact with each other via the nonmetallic conductive agent. This leads to surprisingly good discharge properties of a galvanic element according to the invention.
- the non-metallic conductive agent is preferably contained in the mercury-free negative electrode in a proportion between 0.01% by weight and 5% by weight. Within this range, proportions of between 0.05% by weight and 1.5% by weight, in particular between 0.1% by weight and 0.3% by weight, are more preferred.
- the mercury-free negative electrode of a galvanic element according to the invention "essentially” of the metal or the metal alloy and the non-metallic Leitmitte!
- the limitation “substantially” is to be interpreted in the context of the present invention in that the negative Electrode contains apart from the above-mentioned components only further customary for electrodes additives (of course, apart from mercury) in very small amounts.
- the proportion is such additives in the negative electrode usually at not more than 5 wt .-%. It is preferably less than 1.5% by weight.
- a galvanic element according to the invention has a negative electrode which, in addition to the components mentioned, also comprises a binder as such conventional additive, in particular in a proportion of between 0.01% by weight and 5% by weight. Within this range, proportions between 0.05 wt .-% and 1, 5 wt .-%, in particular between 0.1 wt .-% and 0.3 wt .-%, more preferred.
- the metal or metal alloy for the negative electrode is preferably zinc or a zinc alloy.
- the galvanic element according to the invention may therefore in preferred embodiments be a zinc-air or a silver oxide battery.
- the metal or metal alloy is a hydrogen storage alloy. Suitable for batteries hydrogen storage alloys are known in the art in principle, in question are the so-called AB 5 alloys, so for example an alloy of one or more rare earth metals such as lanthanum and nickel in the ratio 1: 5.
- the hydrogen storage alloy can still one or more other metals included as additives.
- the galvanic element according to the invention may thus also be, for example, a nickel-metal hydride battery, aiso a rechargeable battery.
- the non-metallic conductive agent is preferably a carbon-based conductive agent. Particular preference is given to carbon black and / or graphite, but it is also possible to use carbon black and / or graphite. lenstoffnanotubes (CNTs) possible. Mixtures of two or three of the mentioned carbon modifications can also be used. Suitable carbonaceous conductive materials such as conductive carbon black or conductive graphite are commercially available and need not be explained in detail in the context of the present application. The same applies to the mentioned carbon nanotubes.
- the non-metallic conductive agent itself is preferably substantially completely free of metallic components or impurities. Preferably, it is at least 99.9 wt .-% of carbon.
- binder for the negative electrode can be used on commercially available products.
- a binder based on carboxymethylcellulose and / or based on a carboxymethylcellulose derivative is particularly preferably used.
- the galvanic element according to the invention is a button cell.
- a galvanic element according to the invention preferably has a metallic housing made of two half-parts, namely a cell cup and a cell lid.
- cell cup and cell cover made of nickel-plated steel or of a so-called trimetal (a layer arrangement of three metals).
- trimetal a layer arrangement of three metals.
- steel plates with an inner coating of copper and an outer coating of nickel can be used as the trimetal.
- a galvanic element according to the invention can be produced in particular according to the method described below, which is also the subject of the present invention.
- a method according to the invention is suitable for the production of galvanic elements with mercury-free negative electrodes, such as, for example, the above-described galvanic elements according to the invention.
- the inventive method is characterized in that the negative electrode is made of a powder of metal or metal alloy particles whose surface is at least partially coated with a non-metallic conductive agent.
- the method according to the invention comprises an upstream coating step in which an initial powder of metal or metal alloy particles is mixed intensively with the non-metallic conductive agent.
- Intensive mixing should be understood to mean that the mixing process is carried out in such a way that the surface of the particles of the starting powder is at least partially, in particular completely, covered with the nonmetallic conductive agent after mixing.
- suitable devices which ensure such intensive mixing, e.g. mechanical mixers or mills are used.
- the mean particle size of the metal or the metal alloy particles can be adjusted at the same time.
- the starting particles used are particles having an average particle size between 1 ⁇ m and 500 ⁇ m, in particular between 40 ⁇ m and 400 ⁇ m.
- the resulting particles with surface coated at least partially with the nonmetallic conductive agent also have a particle size in these sem area.
- the particle size can also deviate upwards or downwards.
- the conductive agent is usually used in powder form, in particular, in preferred embodiments, it has an average particle size of between 2 ⁇ m and 20 ⁇ m.
- At least one further additive in particular a binder, can be added to the metal or metal alloy particles in addition to the nonmetallic conductive agents.
- this is preferably done before and / or during the mixing process.
- the mixing process is carried out dry. This is to be understood as meaning that no liquids, in particular no water, are added to the components to be mixed.
- the mixing can be carried out under protective gas in order to protect the mix from atmospheric moisture.
- the powder obtained from the dry mixing process can also be converted into paste form by the addition of electrolyte, but it is preferably further processed dry. So can be made from the powder, for example, a pressing, which can then be installed as a negative electrode.
- the powder for producing a negative electrode can also be sprinkled directly into a housing half part, in particular the negative housing half part of the galvanic element to be produced. In both cases, the addition of electrolyte then takes place afterwards.
- the powder of the metal or metal alloy particles with the at least partially coated surface is particularly well suited for dry processing. It has been found that such powders are characterized by a particularly high lubricity and flowability.
- a zinc powder having an average particle size of about 200 ⁇ m was admixed with a conductive carbon black and carboxymethyl cellulose as binder.
- the proportions of the carbon black and the binder were in each case about 0.15% by weight, the proportion of zinc was about 99.7% by weight.
- the three components became intense in a mechanical mixing device mixed.
- the resulting powder was sprinkled into the cell lid of a button cell casing and treated with an alkaline electrolyte.
- the cell lid was then combined with a suitable seal and then a suitable cell cup containing an air-oxygen electrode. By crimping the cut edge of the cell cup over the edge of the cell lid, the cell was closed.
- the proportion of the binder was about 0.15 wt .-%, the proportion of zinc about 99.85 wt .-%.
- Fig. 1 the Entladediagramm the comparative cell is shown, in Fig. 2 of the galvanic element according to the invention.
- the galvanic element according to the invention provides significantly longer voltage than the comparative cell. This is attributed to the fact that the zinc in the negative electrode of the galvanic element according to the invention is more completely reacted.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Hybrid Cells (AREA)
Abstract
The invention relates to a galvanic element comprising a mercury-free negative electrode, made substantially of a metal or metal alloy and a non-metal conductive agent. The invention further relates to a method for producing a galvanic element, according to which a mercury-free negative electrode is produced from a powder of metal or metal alloy particles, the surface thereof being at least partially coated by a non-metal conductive agent.
Description
Beschreibung description
Galvanisches Element mit quecksilberfreier negativer ElektrodeGalvanic element with mercury-free negative electrode
Die vorliegende Erfindung betrifft ein galvanisches Element, das sich insbesondere durch eine quecksilberfreie negative Elektrode auszeichnet. Des weiteren betrifft die vorliegende Erfindung ein Verfahren, mit dem sich solche galvanische Elemente mit quecksilberfreier negativer Elektrode herstellen lassen.The present invention relates to a galvanic element, which is characterized in particular by a mercury-free negative electrode. Furthermore, the present invention relates to a method with which such galvanic elements can be produced with mercury-free negative electrode.
Galvanische Elemente wie Batterien und Akkumulatoren finden heute in vielerlei Bereichen Verwendung. Sie dienen insbesondere zur Versorgung portabler Geräte mit elektrischer Energie. In sehr kleine Geräte wie Uhren und Hörgeräte werden die galvanischen Elemente vorzugsweise in Form von Knopfzellen eingesetzt. Besonders Hörgeräte weisen einen relativ hohen Stromverbrauch auf. Deswegen werden Hörgeräte in aller Regel mit Batterien des elektrochemischen Systems Zink-Luft versorgt, die sich durch eine besonders hohe Kapazität auszeichnen. Handelsübliche Zink-Luft-Batterien sind nicht wiederaufladbar und müssen entsprechend nach dem Gebrauch entsorgt werden. Dies ist allerdings problematisch, da sie bis zu etwa 1 Gew.-% Quecksilber enthalten können, das nicht in die Umwelt gelangen sollte.Galvanic elements such as batteries and accumulators are used today in many areas. They serve in particular to supply portable devices with electrical energy. In very small devices such as watches and hearing aids, the galvanic elements are preferably used in the form of button cells. Especially hearing aids have a relatively high power consumption. Therefore, hearing aids are usually supplied with batteries of the electrochemical system zinc-air, which are characterized by a particularly high capacity. Commercially available zinc-air batteries are not rechargeable and must be disposed of after use. However, this is problematic because they can contain up to about 1% by weight of mercury which should not be released into the environment.
Quecksilber hat in Elektroden wie z.B. in den Anoden von Zink-Luft- und Silberoxidbatterien u.a. die Funktion, die elektrische Kontaktierung zwischen den einzelnen Zinkpartikeln zu verbessern. Es erhöht somit die interne Gesamtleitfähigkeit der Elektroden. Dies spieit insbesondere bei fortgeschrittenem Entladezustand eine große Rolle. Das leitfähige Aktivmaterial Zink wird nämlich während der Entladung zu nicht leitfähigem Zinkoxid umgewandelt, so dass der Stromleitung innerhalb der Elektrode immer größere Widerstände entgegenstehen. Ohne ausreichenden Zu-
satz von Quecksilber werden somit in der Regel aufgrund schlechter elektrischer Kontaktierung innerhalb einer Elektrode nicht alle Zinkpartikel zu Zinkoxid umgewandelt. Der theoretische Energiegehalt einer Elektrode wird entsprechend nicht vollständig ausgeschöpft.Among other things, mercury in electrodes such as in the anodes of zinc-air and silver oxide batteries has the function of improving the electrical contact between the individual zinc particles. It thus increases the internal overall conductivity of the electrodes. This is particularly important in the case of advanced unloading condition. The conductive active material zinc is namely converted during the discharge to non-conductive zinc oxide, so that the power line within the electrode to resist ever greater resistance. Without sufficient As a rule, due to poor electrical contact within an electrode, not all zinc particles are converted into zinc oxide. The theoretical energy content of an electrode is not fully exploited accordingly.
Nichtsdestotrotz besteht jedoch aufgrund der potentiellen Schädlichkeit von Quecksilber für die Umwelt sowie für die Gesundheit von Mensch und Tier die Notwendigkeit, mittelfristig auf seinen Einsatz gänzlich zu verzichten. Es besteht somit ein Bedarf an galvanischen Elementen, insbesondere solchen vom Knopfzellentyp, die frei von Quecksilber sind.Nonetheless, due to the potential harmfulness of mercury to the environment and to human and animal health, there is a need to avoid using it altogether in the medium term. There is thus a need for galvanic elements, particularly those of the button cell type, which are mercury-free.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, solche galvanische Elemente bereitzustellen. Der Fokus sollte dabei auf der Entwicklung von Elektroden liegen, die im Hinblick auf die angesprochene Problematik der unvollständigen Umsetzung von Zink optimiert sind und die diesbezüglich hinter quecksilberhaltigen Elektroden zumindest nicht wesentlich zurückstehen.The object of the present invention was to provide such galvanic elements. The focus should be on the development of electrodes, which are optimized in view of the mentioned problem of incomplete reaction of zinc and in this respect at least not significantly lag behind electrodes containing mercury.
Diese Aufgabe wird gelöst durch das galvanische Element mit den Merkmalen des Anspruchs 1 sowie das Verfahren zur Herstellung eines galvanischen Elements mit den Merkmalen des Anspruchs 9. Bevorzugte Ausführungsformen des erfindungsgemäßen galvanischen Elements sind in den abhängigen Ansprüchen 2 bis 8 angegeben. Bevorzugte Ausführungsformen des erfindungsgemäßen Verfahrens finden sich in den abhängigen Ansprüchen 10 bis 17. Der Wortlaut sämtlicher Ansprüche wird hiermit durch Bezugnahme zum Inhalt dieser Beschreibung gemacht.This object is achieved by the galvanic element with the features of claim 1 and the method for producing a galvanic element having the features of claim 9. Preferred embodiments of the galvanic element according to the invention are specified in the dependent claims 2 to 8. Preferred embodiments of the method according to the invention can be found in the dependent claims 10 to 17. The wording of all claims is hereby incorporated by reference into the content of this description.
Ein erfindungsgemäßes galvanisches Element umfasst eine quecksilberfreie negative Elektrode, die sich vor allem dadurch auszeichnet, dass sie im wesentlichen nur aus einem Metall oder aus einer Metalllegierung und einem nichtmetallischen Leitmittel besteht.
Überraschenderweise wurde gefunden, dass sich der aus dem Stand der Technik bekannte Anteil an Quecksilber in negativen Elektroden von galvanischen Elementen durch einen Anteil an dem nichtmetallischen Leitmittels ersetzen lässt, ohne dass es dabei zu einer unvollständigen Entladung der Zelle aufgrund von internen Kontaktproblemen in der negativen Elektrode kommt.A galvanic element according to the invention comprises a mercury-free negative electrode, which is distinguished in particular by the fact that it essentially consists only of a metal or a metal alloy and a non-metallic conductive agent. Surprisingly, it has been found that the amount of mercury in negative electrodes known from the prior art can be replaced by galvanic elements by a proportion of the non-metallic conductive agent, without resulting in incomplete discharge of the cell due to internal contact problems in the negative electrode comes.
Besonders bevorzugt besteht die negative Elektrode eines erfindungsgemäßen galvanischen Elements im wesentlichen aus Partikeln aus dem Metall oder der Metalllegierung, deren Oberfläche zumindest teilweise mit dem nichtmetallischen Leitmittel beschichtet ist. In der Elektrode stehen diese einzelnen Partikel - abgesehen von bestehenden direkten Kontakten zwischen den Partikeln - zusätzlich über das nichtmetallische Leitmittel miteinander in elektrischem Kontakt. Dies führt zu erstaunlich guten Entladungseigenschaften eines erfindungsgemäßen galvanischen Elements.Particularly preferably, the negative electrode of a galvanic element according to the invention consists essentially of particles of the metal or the metal alloy, whose surface is at least partially coated with the non-metallic conductive agent. In the electrode, apart from existing direct contacts between the particles, these individual particles are additionally in electrical contact with each other via the nonmetallic conductive agent. This leads to surprisingly good discharge properties of a galvanic element according to the invention.
Das nichtmetallische Leitmittel ist in der quecksilberfreien negativen E- lektrode bevorzugt in einem Anteil zwischen 0,01 Gew.-% und 5 Gew.-% enthalten. Innerhalb dieses Bereiches sind Anteile zwischen 0,05 Gew.- % und 1 ,5 Gew.-%, insbesondere zwischen 0,1 Gew.-% und 0,3 Gew.- %, weiter bevorzugt.The non-metallic conductive agent is preferably contained in the mercury-free negative electrode in a proportion between 0.01% by weight and 5% by weight. Within this range, proportions of between 0.05% by weight and 1.5% by weight, in particular between 0.1% by weight and 0.3% by weight, are more preferred.
Wie oben bereits erwähnt, besteht die quecksilberfreie negative Elektrode eines erfindungsgemäßen galvanischen Elements „im wesentlichen" aus dem Metall bzw. der Metalllegierung und dem nicht metallischen Leitmitte!. Die Einschränkung „im wesentlichen" ist im Rahmen der vorliegenden Erfindung dahingehend auszulegen, dass die negative Elektrode abgesehen von den bereits genannten Komponenten lediglich noch weitere für Elektroden übliche Zusätze (natürlich abgesehen von Quecksilber) in sehr geringen Mengen enthält. Vorzugsweise liegt der Anteil
solcher Zusätze in der negativen Elektrode in der Regel bei nicht mehr als 5 Gew.-%. Bevorzugt beträgt er weniger als 1 ,5 Gew.-%.As already mentioned above, the mercury-free negative electrode of a galvanic element according to the invention "essentially" of the metal or the metal alloy and the non-metallic Leitmitte! The limitation "substantially" is to be interpreted in the context of the present invention in that the negative Electrode contains apart from the above-mentioned components only further customary for electrodes additives (of course, apart from mercury) in very small amounts. Preferably, the proportion is such additives in the negative electrode usually at not more than 5 wt .-%. It is preferably less than 1.5% by weight.
So weist ein erfindungsgemäßes galvanisches Element in bevorzugten Ausführungsformen eine negative Elektrode auf, die neben den erwähnten Komponenten noch einen Binder als solchen üblichen Zusatz um- fasst, diesen insbesondere in einem Anteil zwischen 0,01 Gew.-% und 5 Gew.-%. Innerhalb dieses Bereiches sind Anteile zwischen 0,05 Gew.-% und 1 ,5 Gew.-%, insbesondere zwischen 0,1 Gew.-% und 0,3 Gew.-%, weiter bevorzugt.Thus, in preferred embodiments, a galvanic element according to the invention has a negative electrode which, in addition to the components mentioned, also comprises a binder as such conventional additive, in particular in a proportion of between 0.01% by weight and 5% by weight. Within this range, proportions between 0.05 wt .-% and 1, 5 wt .-%, in particular between 0.1 wt .-% and 0.3 wt .-%, more preferred.
Bei dem Metall oder der Metalllegierung für die negative Elektrode handelt es sich vorzugsweise um Zink oder um eine Zinklegierung. Bei dem erfindungsgemäßen galvanischen Element kann es sich somit in bevorzugten Ausführungsformen um eine Zink-Luft- oder um eine Silberoxidbatterie handeln.The metal or metal alloy for the negative electrode is preferably zinc or a zinc alloy. The galvanic element according to the invention may therefore in preferred embodiments be a zinc-air or a silver oxide battery.
Weiterhin kann es bevorzugt sein, dass es sich bei dem Metall oder der Metalllegierung um eine Wasserstoffspeicherlegierung handelt. Für Batterien geeignete Wasserstoffspeicherlegierungen sind dem Fachmann grundsätzlich bekannt, in Frage kommen insbesondere die sogenannten AB5-Legierungen, also beispielsweise eine Legierung aus einem oder mehreren Seltenerdenmetallen wie Lanthan und Nickel im Verhältnis 1 : 5. Gegebenenfalls kann die Wasserstoffspeicherlegierung noch ein oder mehrere weitere Metalle als Zusätze enthalten. In bevorzugten Ausführungsformen kann es sich bei dem erfindungsgemäßen galvanischen Element also z.B. auch um eine Nickel-Metallhydrid-Batterie handeln, aiso um eine wiederaufiadbare Batterie.Furthermore, it may be preferred that the metal or metal alloy is a hydrogen storage alloy. Suitable for batteries hydrogen storage alloys are known in the art in principle, in question are the so-called AB 5 alloys, so for example an alloy of one or more rare earth metals such as lanthanum and nickel in the ratio 1: 5. Optionally, the hydrogen storage alloy can still one or more other metals included as additives. In preferred embodiments, the galvanic element according to the invention may thus also be, for example, a nickel-metal hydride battery, aiso a rechargeable battery.
Bei dem nichtmetallischen Leitmittel handelt es sich vorzugsweise um ein kohlenstoffbasiertes Leitmittel. Besonders bevorzugt kommen Ruß und/oder Graphit in Frage, es ist jedoch auch der Einsatz von Koh-
lenstoffnanotubes (CNTs) möglich. Auch Mischungen aus zwei oder drei der genannten Kohlenstoffmodifikationen können verwendet werden. Als Leitmittel geeignete Kohlenstoffmaterialien wie Leitruß oder Leitgraphit sind kommerziell erhältlich und müssen im Rahmen der vorliegenden Anmeldung nicht ausführlich erläutert werden. Gleiches gilt auch für die erwähnten Kohlenstoffnanotubes.The non-metallic conductive agent is preferably a carbon-based conductive agent. Particular preference is given to carbon black and / or graphite, but it is also possible to use carbon black and / or graphite. lenstoffnanotubes (CNTs) possible. Mixtures of two or three of the mentioned carbon modifications can also be used. Suitable carbonaceous conductive materials such as conductive carbon black or conductive graphite are commercially available and need not be explained in detail in the context of the present application. The same applies to the mentioned carbon nanotubes.
Das nichtmetallische Leitmittel selbst ist bevorzugt im wesentlichen vollständig frei von metallischen Anteilen bzw. Verunreinigungen. Vorzugsweise besteht es zu mindestens 99,9 Gew.-% aus Kohlenstoff.The non-metallic conductive agent itself is preferably substantially completely free of metallic components or impurities. Preferably, it is at least 99.9 wt .-% of carbon.
Auch betreffend den im Rahmen der vorliegenden Erfindung einsetzbaren Binder für die negative Elektrode kann auf kommerziell erhältliche Produkte zurückgegriffen werden. Besonders bevorzugt kommt vorliegend ein Binder auf Basis von Carboxymethylcellulose und/oder auf Basis eines Carboxymethylcellulose-Derivats zum Einsatz.Also regarding the usable for the purposes of the present invention binder for the negative electrode can be used on commercially available products. In the present case, a binder based on carboxymethylcellulose and / or based on a carboxymethylcellulose derivative is particularly preferably used.
Besonders bevorzugt handelt es sich bei dem erfindungsgemäßen galvanischen Element um eine Knopfzelle. Als solche weist ein erfindungsgemäßes galvanisches Element vorzugsweise ein metallisches Gehäuse aus zwei Halbteilen, nämlich einem Zellenbecher und einem Zellendeckel auf. Besonders geeignet sind Zellenbecher und Zellendeckel aus vernickeltem Stahl oder aus einem sogenannten Trimetall (eine Schichtanordnung aus drei Metallen). Als Trimetall sind insbesondere Stahlbleche mit einer innenliegenden Beschichtung aus Kupfer und einer außenliegenden Beschichtung aus Nickel einsetzbar.Particularly preferably, the galvanic element according to the invention is a button cell. As such, a galvanic element according to the invention preferably has a metallic housing made of two half-parts, namely a cell cup and a cell lid. Particularly suitable are cell cup and cell cover made of nickel-plated steel or of a so-called trimetal (a layer arrangement of three metals). In particular, steel plates with an inner coating of copper and an outer coating of nickel can be used as the trimetal.
Herstellen lässt sich ein erfindungsgemäßes galvanisches Element insbesondere gemäß dem nachstehend beschriebenen Verfahren, das e- benfalls Gegenstand der vorliegenden Erfindung ist.
Ein erfindungsgemäßes Verfahren eignet sich zur Herstellung von galvanischen Elementen mit quecksilberfreien negativen Elektroden wie beispielsweise den oben beschriebenen erfindungsgemäßen galvanischen Elementen.A galvanic element according to the invention can be produced in particular according to the method described below, which is also the subject of the present invention. A method according to the invention is suitable for the production of galvanic elements with mercury-free negative electrodes, such as, for example, the above-described galvanic elements according to the invention.
Das erfindungsgemäße Verfahren zeichnet sich dadurch aus, dass die negative Elektrode aus einem Pulver aus Metall- oder Metalllegierungs- Partikeln hergestellt wird, deren Oberfläche zumindest teilweise mit einem nichtmetallischen Leitmittel beschichtet ist.The inventive method is characterized in that the negative electrode is made of a powder of metal or metal alloy particles whose surface is at least partially coated with a non-metallic conductive agent.
Die zumindest teilweise Beschichtung der Oberfläche der Partikel aus dem Metall oder der Metalllegierung ist dabei ein besonders wichtiger Aspekt. Vorzugsweise umfasst das erfindungsgemäße Verfahren einen vorgeschalteten Beschichtungsschritt, bei dem ein Ausgangspulver aus Metall- oder Metalllegierungspartikeln intensiv mit dem nichtmetallischen Leitmittel gemischt wird.The at least partial coating of the surface of the particles of the metal or the metal alloy is a particularly important aspect. Preferably, the method according to the invention comprises an upstream coating step in which an initial powder of metal or metal alloy particles is mixed intensively with the non-metallic conductive agent.
Unter einem intensiven Mischen soll dabei verstanden werden, dass der Mischvorgang derart vorgenommen wird, dass die Oberfläche der Partikel des Ausgangspulvers nach dem Mischen zumindest teilweise, insbesondere vollständig, mit dem nichtmetallischen Leitmittel bedeckt ist. Als geeignete Vorrichtungen, die eine solche intensive Vermischung gewährleisten, können z.B. mechanische Mischer oder Mühlen zum Einsatz kommen. Insbesondere bei Einsatz Letzterer kann gleichzeitig auch die mittlere Partikelgröße der Metall- bzw. der Metalllegierungspartikel gezielt eingestellt werden.Intensive mixing should be understood to mean that the mixing process is carried out in such a way that the surface of the particles of the starting powder is at least partially, in particular completely, covered with the nonmetallic conductive agent after mixing. As suitable devices which ensure such intensive mixing, e.g. mechanical mixers or mills are used. In particular, when using the latter, the mean particle size of the metal or the metal alloy particles can be adjusted at the same time.
Vorzugsweise werden ais Ausgangspuiver Partikel mit einer mittleren Korngröße zwischen 1 μm und 500 μm, insbesondere zwischen 40 μm und 400 μm, eingesetzt. Abhängig vom Mischvorgang weisen die resultierenden Partikel mit zumindest teilweise mit dem nichtmetallischen Leitmittel beschichteter Oberfläche ebenfalls eine Partikelgröße in die-
sem Bereich auf. Natürlich kann die Partikelgröße aber auch nach oben oder nach unten hin abweichen.Preferably, the starting particles used are particles having an average particle size between 1 μm and 500 μm, in particular between 40 μm and 400 μm. Depending on the mixing process, the resulting particles with surface coated at least partially with the nonmetallic conductive agent also have a particle size in these sem area. Of course, the particle size can also deviate upwards or downwards.
Das Leitmittel wird in der Regel pulverförmig eingesetzt, insbesondere weist es in bevorzugten Ausführungsformen eine mittlere Korngröße zwischen 2 μm und 20 μm auf.The conductive agent is usually used in powder form, in particular, in preferred embodiments, it has an average particle size of between 2 μm and 20 μm.
Entsprechend den obigen Erläuterungen zu den bevorzugten Ausführungsformen eines erfindungsgemäßen galvanischen Elements kann den Metall- oder Metalllegierungs-Partikeln neben den nichtmetallischen Leitmitteln noch mindestens ein weiterer Zusatz, insbesondere ein Binder, zugesetzt werden. Gegebenenfalls erfolgt dies bevorzugt vor und/oder während des Mischvorgangs.According to the above explanations of the preferred embodiments of a galvanic element according to the invention, at least one further additive, in particular a binder, can be added to the metal or metal alloy particles in addition to the nonmetallic conductive agents. Optionally, this is preferably done before and / or during the mixing process.
In bevorzugten Ausführungsformen des erfindungsgemäßen Verfahrens wird der Mischvorgang trocken durchgeführt. Darunter soll verstanden werden, dass den zu mischenden Komponenten keine Flüssigkeiten, insbesondere kein Wasser, zugesetzt wird. In bevorzugten Ausführungsformen kann das Mischen unter Schutzgas erfolgen, um das Mischgut vor Luftfeuchtigkeit zu schützen.In preferred embodiments of the method according to the invention, the mixing process is carried out dry. This is to be understood as meaning that no liquids, in particular no water, are added to the components to be mixed. In preferred embodiments, the mixing can be carried out under protective gas in order to protect the mix from atmospheric moisture.
Natürlich ist es auch möglich, der Mischung aus dem Pulver und dem Leitmittel sowie gegebenenfalls dem mindestens einen weiteren Zusatz vor und/oder während des Mischvorgangs Elektrolytlösung oder eine sonstige Flüssigkeit zuzusetzen. Aus dem Mischvorgang resultiert dann in der Regel eine Paste, die direkt zu einer Elektrode weiterverarbeitet werden kann.Of course, it is also possible to add to the mixture of the powder and the conductive agent and optionally the at least one further additive before and / or during the mixing process electrolyte solution or another liquid. From the mixing process then usually results in a paste that can be further processed directly to an electrode.
Das aus dem trocken durchgeführten Mischvorgang erhaltene Pulver kann durch Zusatz von Elektrolyt natürlich ebenfalls in Pastenform überführt werden, vorzugsweise wird es jedoch trocken weiterverarbeitet. So
kann aus dem Pulver z.B. ein Pressung hergestellt werden, der anschließend als negative Elektrode verbaut werden kann.Of course, the powder obtained from the dry mixing process can also be converted into paste form by the addition of electrolyte, but it is preferably further processed dry. So can be made from the powder, for example, a pressing, which can then be installed as a negative electrode.
In bevorzugten Ausführungsformen des erfindungsgemäßen Verfahrens kann das Pulver zur Herstellung einer negativen Elektrode auch unmittelbar in ein Gehäusehalbteil, insbesondere das negative Gehäusehalbteil des herzustellenden galvanischen Elements, eingerieselt werden. In beiden Fällen erfolgt dann anschließend noch der Zusatz von Elektrolyt.In preferred embodiments of the method according to the invention, the powder for producing a negative electrode can also be sprinkled directly into a housing half part, in particular the negative housing half part of the galvanic element to be produced. In both cases, the addition of electrolyte then takes place afterwards.
Das Pulver aus den Metall- oder Metalllegierungs-Partikeln mit der zumindest teilweise beschichteten Oberfläche eignet sich besonders gut zur trockenen Weiterverarbeitung. Es wurde gefunden, dass sich solche Pulver durch eine besonders hohe Gleit- und Rieselfähigkeit auszeichnen.The powder of the metal or metal alloy particles with the at least partially coated surface is particularly well suited for dry processing. It has been found that such powders are characterized by a particularly high lubricity and flowability.
Die genannten und weitere Vorteile der Erfindung ergeben sich aus der nun folgenden Beschreibung von bevorzugten Ausführungsformen in Verbindung mit den Zeichnungen und den Unteransprüchen. Dabei können die einzelnen Merkmale der Erfindung für sich allein oder in Kombination miteinander verwirklicht sein. Die beschriebenen Ausführungsformen dienen lediglich zur Erläuterung und zum besseren Verständnis der Erfindung und sind in keiner Weise einschränkend zu verstehen.The above and other advantages of the invention will become apparent from the following description of preferred embodiments in conjunction with the drawings and the dependent claims. In this case, the individual features of the invention can be implemented alone or in combination with each other. The described embodiments are merely illustrative and for a better understanding of the invention and are in no way limiting.
Beispielexample
Zur Herstellung eines erfindungsgemäßen galvanischen Elementes wurde ein Zinkpulver mit einer mittleren Korngröße von ca. 200 μrn mit einem Leitruß und Carboxymethylzellulose als Binder versetzt. Die Anteile an dem Ruß und dem Binder betrugen dabei jeweils ca. 0,15 Gew.- %, der Anteil an Zink betrug ca. 99,7 Gew.-%. Die drei Komponenten wurden in einer mechanischen Mischvorrichtung intensiv miteinander
vermischt. Anschließend wurde das dabei erhaltene Pulver in den Zellendeckel eines Knopfzellengehäuses eingerieselt und mit einem alkalischen Elektrolyten versetzt. Der Zellendeckel wurde anschließend mit einer geeigneten Dichtung sowie anschließend einem passenden, eine Luft-Sauerstoff-Elektrode enthaltenden Zellenbecher kombiniert. Durch Umbördeln der Schnittkante des Zellenbechers über den Rand des Zellendeckel wurde die Zelle verschlossen.To produce a galvanic element according to the invention, a zinc powder having an average particle size of about 200 μm was admixed with a conductive carbon black and carboxymethyl cellulose as binder. The proportions of the carbon black and the binder were in each case about 0.15% by weight, the proportion of zinc was about 99.7% by weight. The three components became intense in a mechanical mixing device mixed. Subsequently, the resulting powder was sprinkled into the cell lid of a button cell casing and treated with an alkaline electrolyte. The cell lid was then combined with a suitable seal and then a suitable cell cup containing an air-oxygen electrode. By crimping the cut edge of the cell cup over the edge of the cell lid, the cell was closed.
Zur Herstellung einer Vergleichszelle wurde analog vorgegangen, allerdings wurde kein Ruß zugesetzt. Der Anteil an dem Binder betrug ca. 0,15 Gew.-%, der Anteil an Zink ca. 99,85 Gew.-%.To prepare a comparative cell was carried out analogously, but no carbon black was added. The proportion of the binder was about 0.15 wt .-%, the proportion of zinc about 99.85 wt .-%.
Mit dem erfindungsgemäßen galvanischen Element sowie mit einer Vergleichszelle wurden Entladungsuntersuchungen vorgenommen. Die Ergebnisse dieser Untersuchungen sind in den Zeichnungen dargestellt.Discharge investigations were made with the galvanic element according to the invention and with a comparative cell. The results of these investigations are shown in the drawings.
In Fig. 1 ist das Entladediagramm der Vergleichszelle dargestellt, in Fig. 2 das des erfindungsgemäßen galvanischen Elements. Wie sofort zu erkennen ist, liefert das erfindungsgemäße galvanische Element deutlich länger Spannung als die Vergleichszelle. Dies wird darauf zurückgeführt, dass das Zink in der negativen Elektrode des erfindungsgemäßen galvanischen Elements vollständiger umgesetzt wird.
In Fig. 1, the Entladediagramm the comparative cell is shown, in Fig. 2 of the galvanic element according to the invention. As can be seen immediately, the galvanic element according to the invention provides significantly longer voltage than the comparative cell. This is attributed to the fact that the zinc in the negative electrode of the galvanic element according to the invention is more completely reacted.
Claims
1. Galvanisches Element, insbesondere Knopfzelle, umfassend eine quecksilberfreie negative Elektrode, die im wesentlichen aus einem Metall oder aus einer Metalllegierung und einem nichtmetallischen Leitmittel besteht.A galvanic cell, in particular button cell, comprising a mercury-free negative electrode consisting essentially of a metal or a metal alloy and a non-metallic conductive agent.
2. Galvanisches Element nach Anspruch 1 , dadurch gekennzeichnet, dass die negative Elektrode im wesentlichen aus Partikeln aus dem Metall oder der Metalllegierung besteht, deren Oberfläche zumindest teilweise mit dem nichtmetallischen Leitmittel beschichtet ist.2. Galvanic element according to claim 1, characterized in that the negative electrode consists essentially of particles of the metal or the metal alloy, whose surface is at least partially coated with the non-metallic conductive agent.
3. Galvanisches Element nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass die negative Elektrode das nichtmetallische Leitmittel in einem Anteil zwischen 0,01 Gew.-% und 5 Gew.-%, vorzugsweise zwischen 0,05 Gew.-% und 1 ,5 Gew.-%, insbesondere zwischen 0,1 Gew.% und 0,3 Gew.-%, aufweist.3. Galvanic element according to claim 1 or claim 2, characterized in that the negative electrode, the non-metallic conductive agent in a proportion of between 0.01 wt .-% and 5 wt .-%, preferably between 0.05 wt .-% and 1 , 5 wt .-%, in particular between 0.1 wt.% And 0.3 wt .-%, having.
4. Galvanisches Element nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die negative Elektrode einen Binder, insbesondere in einem Anteil zwischen 0,01 Gew.-% und 5 Gew.- %, vorzugsweise zwischen 0,05 Gew.-% und 1 ,5 Gew.-%, insbesondere zwischen 0,1 Gew.% und 0,3 Gew.-%, aufweist.4. Galvanic element according to one of claims 1 to 3, characterized in that the negative electrode is a binder, in particular in a proportion between 0.01 wt .-% and 5 wt%, preferably between 0.05 wt .-% and 1, 5 wt .-%, in particular between 0.1 wt.% And 0.3 wt .-%, having.
5. Galvanisches Element nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass dass es sich bei dem Metall oder der Metaiiiegierurig urn Zink, eine Zinkiegierung oder eine Wasserstoffspeicherlegierung handelt.5. Galvanic element according to one of the preceding claims, characterized in that it is the metal or the Metaiiiegierurig to zinc, a Zinkiegierung or a hydrogen storage alloy.
6. Galvanisches Element nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das nichtmetallische Leitmittel ausgewählt ist aus der Gruppe mit Russ, Graphit, Kohlenstoffna- notubes (CNTs) und Mischungen dieser Kohlenstoffmodifikationen.6. Galvanic element according to one of the preceding claims, characterized in that the non-metallic conductive agent is selected from the group consisting of carbon black, graphite, carbon nanotubes (CNTs) and mixtures of these carbon modifications.
7. Galvanisches Element nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das nichtmetallische Leitmittel im wesentlichen frei von metallischen Verunreinigungen ist.7. Galvanic element according to one of the preceding claims, characterized in that the non-metallic conductive agent is substantially free of metallic impurities.
8. Galvanisches Element nach einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, dass es sich bei dem Binder um Carboxy- methylzellulose und/oder ein Derivat davon handelt.8. Galvanic element according to one of claims 4 to 7, characterized in that it is the binder to carboxymethylcellulose and / or a derivative thereof.
9. Verfahren zur Herstellung eines galvanischen Elements mit einer quecksilberfreien negativen Elektrode, insbesondere eines galvanischen Elements nach einem der vorhergehenden Ansprüche, wobei die negative Elektrode aus einem Pulver aus Metall- oder Metalllegierungspartikeln hergestellt wird, deren Oberfläche zumindest teilweise mit einem nichtmetallischen Leitmittel beschichtet ist.9. A method for producing a galvanic cell having a mercury-free negative electrode, in particular a galvanic cell according to any one of the preceding claims, wherein the negative electrode is made of a powder of metal or metal alloy particles whose surface is at least partially coated with a non-metallic conductive agent.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass zur mindestens teilweisen Beschichtung der Partikeloberfläche ein Ausgangspulver aus Metall- oder Metalllegierungspartikeln mit dem nichtmetallischen Leitmittel intensiv gemischt wird.10. The method according to claim 9, characterized in that for at least partial coating of the particle surface, a starting powder of metal or metal alloy particles is mixed intensively with the non-metallic conductive agent.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass das Ausgangspulver Partikel mit einer mittleren Korngröße zwischen 1 μm und 500 μm, insbesondere zwischen 40 μm und 400 μm, aufweist.11. The method according to claim 10, characterized in that the starting powder particles having an average particle size between 1 .mu.m and 500 .mu.m, in particular between 40 .mu.m and 400 .mu.m.
12. Verfahren nach einem der Ansprüche 10 oder 11 , dadurch gekennzeichnet, dass das Leitmittel pulverförmig, insbesondere mit einer mittleren Korngröße zwischen 2 μm und 20 μm, eingesetzt wird.12. The method according to any one of claims 10 or 11, characterized in that the conductive agent in powder form, in particular with a mean particle size between 2 microns and 20 microns, is used.
13. Verfahren nach einem der Ansprüche 10 bis 12, dadurch gekennzeichnet, dass den Metall- oder Metalllegierungspartikeln neben dem nichtmetallischen Leitmittel noch mindestens ein weiterer Zusatz, insbesondere ein Binder, zugesetzt wird, bevorzugt vor und/oder während des Mischvorgangs.13. The method according to any one of claims 10 to 12, characterized in that the metal or metal alloy particles in addition to the non-metallic conductive agent at least one further additive, in particular a binder is added, preferably before and / or during the mixing process.
14. Verfahren nach einem der Ansprüche 10 bis 13, dadurch gekennzeichnet, dass der Mischvorgang trocken durchgeführt wird.14. The method according to any one of claims 10 to 13, characterized in that the mixing operation is carried out dry.
15. Verfahren nach einem der Ansprüche 10 bis 13, dadurch gekennzeichnet, dass der Mischung aus dem Pulver und dem Leitmittel vor und/oder während des Mischvorgangs Elektrolytlösung zugesetzt wird.15. The method according to any one of claims 10 to 13, characterized in that the mixture of the powder and the conductive agent is added before and / or during the mixing process electrolyte solution.
16. Verfahren nach einem der Ansprüche 9 bis 15, dadurch gekennzeichnet, dass das Pulver aus den Metall- oder Metalllegierungspartikeln mit der zumindest teilweise beschichteten Oberfläche trocken oder als Paste verarbeitet wird.16. The method according to any one of claims 9 to 15, characterized in that the powder of the metal or metal alloy particles with the at least partially coated surface is processed dry or as a paste.
17. Verfahren nach einem der Ansprüche 9 bis 16, dadurch gekennzeichnet, dass das Pulver aus Metall- oder Metalllegierungspartikeln mit der zumindest teilweise beschichteten Oberfläche zur Herstellung der negativen Elektrode in ein negatives Gehäusehalbteil des herzustellenden galvanischen Elements eingerieselt wird. 17. The method according to any one of claims 9 to 16, characterized in that the powder of metal or metal alloy particles is drizzled with the at least partially coated surface for the preparation of the negative electrode in a negative Gehäusehalbteil of the produced galvanic element.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102009023126A DE102009023126A1 (en) | 2009-05-20 | 2009-05-20 | Galvanic element with mercury-free negative electrode |
PCT/EP2010/003012 WO2010133331A1 (en) | 2009-05-20 | 2010-05-17 | Galvanic element having a mercury-free negative electrode |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2433324A1 true EP2433324A1 (en) | 2012-03-28 |
Family
ID=42670637
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10721708A Withdrawn EP2433324A1 (en) | 2009-05-20 | 2010-05-17 | Galvanic element having a mercury-free negative electrode |
Country Status (7)
Country | Link |
---|---|
US (1) | US20120070739A1 (en) |
EP (1) | EP2433324A1 (en) |
JP (1) | JP2012527717A (en) |
KR (1) | KR20120018135A (en) |
CN (1) | CN102439762A (en) |
DE (1) | DE102009023126A1 (en) |
WO (1) | WO2010133331A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6246999B2 (en) * | 2011-08-23 | 2017-12-13 | 株式会社日本触媒 | Zinc negative electrode mixture and battery using the zinc negative electrode mixture |
EP2722913B1 (en) * | 2012-10-17 | 2018-11-28 | VARTA Microbattery GmbH | Anode mixture, button cell with an anode comprising a metal particle and their preparation |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58175264A (en) * | 1982-04-06 | 1983-10-14 | Citizen Watch Co Ltd | Manufacture of sealed small battery |
JPS6158165A (en) * | 1984-08-29 | 1986-03-25 | Toshiba Battery Co Ltd | Gelled negative electrode of nommercury sealed alkaline battery |
JPH0763005B2 (en) * | 1987-02-10 | 1995-07-05 | 松下電器産業株式会社 | Sealed alkaline storage battery |
JPH0736333B2 (en) * | 1987-04-23 | 1995-04-19 | 松下電器産業株式会社 | Sealed alkaline storage battery |
DE4017884A1 (en) * | 1990-06-02 | 1991-12-05 | Varta Batterie | GAS-TIGHT ALKALINE ACCUMULATOR |
JPH11283623A (en) * | 1998-03-31 | 1999-10-15 | Sanyo Electric Co Ltd | Lithium ion battery and its manufacture |
JP3173594B2 (en) * | 1998-08-31 | 2001-06-04 | 株式会社ファインセル | Zinc sulfate aqueous solution secondary battery to which manganese salt (II) and carbon powder are added |
TW508861B (en) * | 2000-08-08 | 2002-11-01 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery and positive electrode for the same |
JP2004087264A (en) * | 2002-08-26 | 2004-03-18 | Mitsui Mining & Smelting Co Ltd | Negative electrode material for non-water electrolysis liquid secondary battery, and its manufacturing method |
CN2671134Y (en) * | 2004-04-26 | 2005-01-12 | 四会永利五金电池有限公司 | Alkali non-mercury button battery |
CN2718792Y (en) * | 2004-08-02 | 2005-08-17 | 比亚迪股份有限公司 | Electrode separator for zinc negative electrode accumulator |
CN100367543C (en) * | 2004-08-17 | 2008-02-06 | 比亚迪股份有限公司 | Lithium alloy composite material and its preparing method, minus pole material, negative pole structure and lithium secondary cells |
JP4851707B2 (en) * | 2004-12-15 | 2012-01-11 | セイコーインスツル株式会社 | Method for producing alkaline battery |
EP1962357B1 (en) * | 2006-06-28 | 2013-01-16 | Panasonic Corporation | Alkaline dry battery |
DE102007009295A1 (en) * | 2007-02-16 | 2008-08-21 | Varta Microbattery Gmbh | Galvanic element with high capacity |
JP5116140B2 (en) * | 2007-03-19 | 2013-01-09 | 日立マクセルエナジー株式会社 | Flat silver oxide battery |
-
2009
- 2009-05-20 DE DE102009023126A patent/DE102009023126A1/en not_active Withdrawn
-
2010
- 2010-05-17 WO PCT/EP2010/003012 patent/WO2010133331A1/en active Application Filing
- 2010-05-17 EP EP10721708A patent/EP2433324A1/en not_active Withdrawn
- 2010-05-17 JP JP2012511186A patent/JP2012527717A/en active Pending
- 2010-05-17 KR KR1020117025823A patent/KR20120018135A/en not_active Application Discontinuation
- 2010-05-17 US US13/319,358 patent/US20120070739A1/en not_active Abandoned
- 2010-05-17 CN CN201080022597XA patent/CN102439762A/en active Pending
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2010133331A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE102009023126A1 (en) | 2010-11-25 |
KR20120018135A (en) | 2012-02-29 |
US20120070739A1 (en) | 2012-03-22 |
CN102439762A (en) | 2012-05-02 |
WO2010133331A1 (en) | 2010-11-25 |
JP2012527717A (en) | 2012-11-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE69516351T2 (en) | Secondary lithium solid-state battery | |
DE69712189T2 (en) | ZIN CAN ANODE FOR ELECTROCHEMICAL CELL | |
DE69527612T2 (en) | HIGH FREQUENCY ENERGY CELL | |
DE102018222129A1 (en) | Cathode unit and method for manufacturing a cathode unit | |
EP2759009A1 (en) | Gas diffusion layer with improved electrical conductivity and gas permeability | |
DE10242911A1 (en) | Electrode catalyst for fuel cell and method for its production | |
DE102011004233A1 (en) | Electrodes for batteries, in particular for lithium-ion batteries, and their manufacture | |
DE2623003A1 (en) | ELECTRODE MATERIAL BASED ON LANTHANE AND NICKEL AND ITS ELECTROCHEMICAL APPLICATION | |
DE2738386C3 (en) | Pressed nickel electrode for galvanic elements | |
DE69933596T2 (en) | Non-sintered nickel electrode | |
EP0802574B1 (en) | Additives for manganese dioxide cathodes of primary alkaline cells | |
DE2951167A1 (en) | ELECTROCHEMICAL PRIMARY CELL AND METHOD FOR PRODUCING A CATHODE CURRENT COLLECTOR THEREFOR | |
EP2122710B1 (en) | Galvanic element with a high capacity | |
DE112016006923T5 (en) | A process for producing a negative electrode material of a battery, lithium ion battery and solid state battery | |
EP2433324A1 (en) | Galvanic element having a mercury-free negative electrode | |
DE102018222142A1 (en) | Method for producing a solid electrolyte membrane or an anode and solid electrolyte membrane or an anode | |
EP3144999A1 (en) | Use of electrochemical cells with an electrode made of zinc or a zinc alloy and a portion of aluminium hydroxide and / or at least one aluminate | |
EP3331073B1 (en) | Secondary cell, battery comprising one or more secondary cells and a method for loading and discharging | |
EP2720304B1 (en) | Electrochemical cell with zinc indium electrode | |
EP2985820B1 (en) | Gas diffusion electrode, method for producing a gas diffusion electrode and battery | |
EP1188195B1 (en) | Electrode capable of storing hydrogen and a method for the production of the same | |
EP3384544B1 (en) | Metal particles suitable for producing an anode, production of an anode, anode produced and electrochemical cell having the anode produced | |
DE3822539C2 (en) | Process for producing a negative storage electrode for alkaline batteries | |
EP2722913B1 (en) | Anode mixture, button cell with an anode comprising a metal particle and their preparation | |
DE102023116764A1 (en) | ELECTRODE, SOLID STATE BATTERY AND METHOD FOR PRODUCING THE ELECTRODE |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20111017 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20170626 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20171107 |