US20110159342A1 - Anode and a method of manufacturing an anode - Google Patents

Anode and a method of manufacturing an anode Download PDF

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Publication number
US20110159342A1
US20110159342A1 US13/062,521 US200913062521A US2011159342A1 US 20110159342 A1 US20110159342 A1 US 20110159342A1 US 200913062521 A US200913062521 A US 200913062521A US 2011159342 A1 US2011159342 A1 US 2011159342A1
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United States
Prior art keywords
anode
ink
battery
active material
separator
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.)
Abandoned
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US13/062,521
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English (en)
Inventor
Xiachang Zhang
Li Shoujun
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Enfucell Oy
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Enfucell Oy
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Filing date
Publication date
Priority claimed from FI20085838A external-priority patent/FI122503B/fi
Priority claimed from FI20085840A external-priority patent/FI122947B/fi
Application filed by Enfucell Oy filed Critical Enfucell Oy
Assigned to ENFUCELL OY reassignment ENFUCELL OY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SHOUJUN, LI, ZHANG, XIACHANG
Publication of US20110159342A1 publication Critical patent/US20110159342A1/en
Abandoned legal-status Critical Current

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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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/0402—Methods of deposition of the material
    • 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
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • 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
    • 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/40—Printed batteries, e.g. thin film batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y10T29/49115—Electric battery cell making including coating or impregnating

Definitions

  • the invention is concerned with an anode for a thin battery and a method for preparing such an anode.
  • the basic components of a battery are the electrodes with terminals (electric connections) to connect to an external circuit, a separator to keep the electrodes apart and prevent them from shorting, the electrolyte which carries the charged ions resulting from the chemical reactions taking place at the electrodes and a cover to contain the active chemicals and hold the electrodes in place.
  • “Wet” cells refer to galvanic cells where the electrolyte is in liquid form and is allowed to flow freely within the cell casing. “Dry” cells are cells that use a solid or powdery electrolyte. Cells with liquid electrolyte can be classified as “dry” if the electrolyte is immobilized by some mechanism, such as by gelling it or by holding it in place with an absorbent substance such as paper.
  • the most common type of battery used today is the “dry cell” battery used in e.g. relatively large batteries such as “flashlight” batteries and in miniaturized versions used for wristwatches or calculators.
  • Batteries are often classified by the type of electrolyte used in their construction. There are three common classifications; acid, mildly acid, and alkaline.
  • One battery type consists of a layered structure, i.e. those called thin film batteries.
  • Thin film batteries which term in this text is to be understood as “layered-structured batteries” regardless of size, can be applied directly onto film applications in any shape or size, and flexible batteries can be made by printing on to paper, plastics, or other kind of thin foil.
  • Thin film batteries have e.g. a wide range of uses as power sources for consumer products and for micro-sized applications. Thin film batteries are also suitable for powering smart cards and Radio Frequency IDentification (RFID) tags.
  • RFID Radio Frequency IDentification
  • Methods for manufacturing such a thin battery can e.g. in accordance with the Finnish patent application of the applicant 20070584 includes wetting a separator paper with an electrolyte solution and applying an anode material and a cathode material as pastes on the separator paper(s), the anode paste on one side and the cathode paste on the opposite side.
  • the anode and cathode materials can be applied on the separator papers with different methods such as by coating or printing.
  • the coating and printing processes generally involve the application of a thin film of functional material to a substrate, such as roll of paper, fabric, film or other textile.
  • paste it is in this text just meant, a viscous water-based dispersion of materials.
  • the outmost separator layers will always contain electrolyte, since they absorb electrolyte from the wetted layer and furthermore, the electrolyte solution, that contains additives, might also be mixed with the anode active material and cathode active materials to form so called anode and cathode pastes.
  • the electrodes of a thin battery are formed of the anode and the cathode.
  • the anode material is a paste or ink containing an anode active material and usually electrolyte solution with additives and the cathode material is a paste or ink containing a cathode active material and usually electrolyte solution with additives.
  • the paste is quite viscous so that the electrolyte is not capable of flowing out.
  • the anode active material is often zinc (Zn) and the cathode active material is manganese dioxide (MnO 2 ).
  • the electrolyte solution can e.g. contain ZnCl 2 as a main ingredient as well as additives, such as binder(s).
  • the additive(s) in the electrolyte comprises binder(s) in order to provide other properties to the electrolyte solution for example binding the electrode material particles together to form a paste.
  • the binder is e.g. polyvinylalcohol (PVA).
  • Conductive material is added to the anode and cathode pastes.
  • the conductive material can be carbon powder, such as graphite powder, soot, carbon black, carbon nanotube, conductive ink or combinations thereof.
  • the electrodes (consisting of the anode and cathode pastes inclusive the conductive material) are connected to a collector material and the whole product is covered by films of sealing material.
  • the sealing material can be of e.g. polypropylene, polyethylene, polyester or other known film materials.
  • the collector material is formed to have terminals to be connected to an external circuit.
  • the collector material can be conductive carbon ink, carbon film or other material, which is chemically inert but conductive enough for the purpose.
  • the combined layers are cut in desired sizes to form products.
  • US patent application 2006/0216586 is presented as prior art. It discloses a thin electrochemical cell.
  • the anode of the cell can be a zinc strip.
  • the problem with this solution is, however, that the connection of the zinc strip to the collector is problematic and that the zinc self discharge is high because of lacking coverage.
  • U.S. Pat. No. 6,379,835 is concerned with a thin film battery.
  • the anode is hydrophilic being a water based zinc ink or a zinc ink in an organic solvent+water swellable polymer mixture and therefore the battery has high self discharge rate. Furthermore because of the low conductivity of the anode, an extra collector at the anode is needed.
  • US patent application 2006/0115717 presents a flexible thin printed battery.
  • a conductive aqueous zinc material to constitute the anode is printed directly onto a non-conductive substrate and is made sufficiently conductive to eliminate the need for a distinct anode current collector.
  • the necessary conductivity is achieved by excess zinc+2 cations (from zinc acetate) and polymeric binder (polyvinylpyrrolidone) to improve particle contact.
  • the hydrophilic zinc anode causes high zinc self discharge and unstable conductivity during the discharging process.
  • the object of the invention is to solve the above discussed problems.
  • the anode material of the invention for use in a printed battery comprises a substrate, an anode active material, a conductive material, a binder.
  • the conductive material, the anode active material, the solvent and the binder have been selected to form a film on the substrate at drying after mixing.
  • the method of the invention for manufacturing an anode material for use in a printed battery comprises providing a substrate, an anode active material, a conductive material, a solvent, and a binder.
  • the method further comprises mixing said solvent, said binder, said anode active material and said conductive material to form anode ink, applying said anode ink on said substrate, drying said anode ink on said substrate. In response to said drying, said solvent evaporates and said anode ink forms a film on said substrate.
  • the present invention may be suitable for alternate anode active components, such as magnesium, cadmium, and copper, in combination with conductive material such as carbon ink.
  • the anode active material is zinc (Zn).
  • Water or electrolyte is needed for any electrode reaction and ionic transfer between the electrodes of a battery.
  • Zinc is more easily oxidized in water or in an electrolyte environment than in a dry environment.
  • the zinc anode is therefore made of an aqueous paste of zinc or of a hydrophilic material.
  • the disadvantage of such a prior art battery is, however, that the self discharge is fast. As a consequence of the self-discharge, the lifetime of the battery becomes short and its capacity smaller.
  • the anode is hydrophobic and dry, which makes it difficult for water or electrolyte to directly penetrate into the deep layer of the zinc anode.
  • the hydrophobic layer in the dry anode of the invention works like a wall to keep the moisture level of the battery stable.
  • a suitable moisture level in the battery is of course important for good performance, and when using an anode according to the invention in a battery, the water can transfer from the cathode to the surface of the anode after combination of the different layers.
  • the oxidation reaction takes place at the surface of the anode between the anode active metal, electrolyte and water.
  • the core of the invention is that dry anode ink is used instead of wet/humid anode paste and a separate anode collector as used in prior art.
  • the dry anode ink can (after drying) also provide for the transfer of electrons from the anode material to the ( ⁇ ) terminal on the surface of the battery.
  • the anode of the invention is flexible, stable and mass producible and useful in batteries used as a power source for many applications, where a thin flexible disposal power source is needed.
  • the anode electrode consists of an anode material, which is a homogenous blend of zinc powder and conductive carbon ink.
  • the anode material, for the battery of the invention is prepared by adding zinc powder to conductive carbon ink and by stirring until a homogeneous mixture is obtained.
  • the zinc powder used for this purpose can be a commercial battery grade product with certain properties with respect to the particle size and purity. A particle size less than 50 ⁇ m and purity over 99% have been found suitable. Examples of usable commercial zinc powders are e.g. Grillo-Werke Aktiengesellschaft GZN 3-0 and Xstrata EC-100.
  • the conductive carbon ink used can be a commercial product with certain properties.
  • the ink to be used should possess high conductivity, high flexibility, high binding strength and high hydrophobicity.
  • Examples of usable commercial conductive carbon ink are e.g. XZ302-1 HV and XZ302-1 MV Conductive Carbon, 26-8203 Conductive Graphite, Creative Material 116-19 Low Temperature Curing Conductive Ink, DuPont 7105 Carbon, Asahi FTU-20D3, and Acheson EB-412.
  • the conductive ink and the proportion of zinc and the conductive ink chosen depend on the properties of the materials, e.g. the conductive carbon ink sheet resistance, the conductive carbon ink flexibility, binding strength, viscosity and conductive carbon ink hydrophobic properties.
  • the anode of the invention to be used in a battery has the following advantages for many applications of interest
  • FIG. 1 presents some property test results of the anode used in the invention made with different zinc powders and conductive inks.
  • the anode material is a homogenous blend of zinc powder and conductive carbon ink.
  • An anode material printed on separator produced in advance e.g. in the way presented in PREPARATION EXAMPLE 1 by means of some printing method known in itself on a web of paper supported by a compression roll.
  • the web on which the anode material is printed goes through a nip formed of a compression roll and another printing roll on which the printed anode material is. Thereafter the web is dried.
  • Different known methods can be used in the process, e.g. screen printing, Gravue printing, offset printing, and flexo printing can be used as printing method. Also drying can be performed by heat curing, IR curing and UV curing, and by the force of hot air.
  • the anode material might be cut, and then the cutting method may be e.g. die cutting, laser cutting, perforating, slitting, punching or other known method.
  • the anode material (i.e. anode ink) of the invention is prepared by adding zinc powder to conductive carbon ink and keeping stirring until homogeneous as mentioned early.
  • the ink and zinc powder used in the test are Acheson EB 412 and EC-100.
  • the conductive carbon ink is stirred with a speed of e.g. 300 rpm and the zinc powder is added gradually.
  • the speed of the mixer is gradually increased up to 2000 rpm and the blend is further stirred in about 30 minutes.
  • the mixing in the way it is done in the invention gives a good result of anode performance, since peeling problems, conductivity problems an uneven conductivity is avoided.
  • a proper viscosity of the anode material is needed. If the viscosity is too low, then zinc particles will deposit to the bottom.
  • a suitable viscosity of the ink is: Brookfield 20° C. 20 RPM 20000 mPaS to 28000 mPa ⁇ S.
  • the mixing quality can be controlled by taking samples and checking their density or can be measured by electronic microscope.
  • anode material i.e. anode ink
  • it can be printed and dried in advance and e.g. be stored on rolls after printing on separator.
  • anode ink Some properties of the anode material (i.e. anode ink) can be seen as indications of the quality for a battery to be made:
  • the hydrophobicity was evaluated by applying water on the anode, and the hydrophobicity was considered good if the water did not dissolve, the anode did not break and/or the sheet resistance did not change
  • V O is the open loop voltage of the battery
  • V L is the voltage of load, which is measured 1 minute late after discharge starts
  • R L is the resistance value of the load, the internal resistance
  • R in ( V ⁇ ⁇ O - V ⁇ ⁇ L ) ⁇ R ⁇ ⁇ L V ⁇ ⁇ L
  • Sheet resistance is measured after conductive ink or anode ink is printed on a substrate and dried.
  • the sheet resistance value is the average resistance value at 6 different positions on the sheet. Each resistance is measured by using two probes of multimeter through a distance of 1 cm.
  • Anode inks made by different proportions of zinc powder and conductive carbon ink were made by the method of preparation example 1.
  • the zinc powders used in the tests were:
  • A Grillo-Werke Aktiengesellschaft GZN 3-0 (Zinc content 99.8%, particle size >25 ⁇ m 14%, ⁇ 25 ⁇ m 86%) and B: Xstrata EC-100 (Zinc content 99.9%, particle size >75 ⁇ m 0.1%, ⁇ 45 ⁇ m 96%).
  • the conductive carbon ink used were
  • FIG. 1 shows the test results on the flexibility, on the hydrophobicity and on the sheet resistance of the anode inks.
  • the FIGURE shows that, for all anode inks tested, the object of the invention is fulfilled regarding hydrophobicity even for sheet resistances up to 80 ⁇ .
  • the results in the table in FIG. 1 show that the advantageous properties of anode ink mainly rely on which conductive ink is used. Inks E and G have better properties and their related zinc anode do not depend on the zinc powder used. The anode using ink G is the best with a sheet resistance of 25 ⁇ . Ink G was used in the test below.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Primary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
US13/062,521 2008-09-08 2009-09-04 Anode and a method of manufacturing an anode Abandoned US20110159342A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FI20085838 2008-09-08
FI20085840 2008-09-08
FI20085838A FI122503B (fi) 2008-09-08 2008-09-08 Painettu ohutparisto ja menetelmä painetun ohutpariston valmistamiseksi
FI20085840A FI122947B (fi) 2008-09-08 2008-09-08 Anodi ja menetelmä anodin valmistamiseksi
PCT/FI2009/000081 WO2010026285A1 (en) 2008-09-08 2009-09-04 Anode and a method of manufacturing an anode

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US20110159342A1 true US20110159342A1 (en) 2011-06-30

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US13/062,520 Active 2029-10-02 US8574742B2 (en) 2008-09-08 2009-09-04 Battery and a method of manufacturing a battery
US13/062,521 Abandoned US20110159342A1 (en) 2008-09-08 2009-09-04 Anode and a method of manufacturing an anode

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Application Number Title Priority Date Filing Date
US13/062,520 Active 2029-10-02 US8574742B2 (en) 2008-09-08 2009-09-04 Battery and a method of manufacturing a battery

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US (2) US8574742B2 (ko)
EP (1) EP2335306A4 (ko)
JP (1) JP2012502416A (ko)
KR (1) KR20110053256A (ko)
CN (2) CN102150310A (ko)
WO (2) WO2010026286A1 (ko)

Cited By (1)

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US20160181952A1 (en) * 2014-12-19 2016-06-23 Samsung Electronics Co., Ltd. Energy generating device, and method of manufacturing the same

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FI20095728A0 (fi) * 2009-06-26 2009-06-26 Enfucell Ltd Menetelmä ohuiden paristojen valmistamiseksi
CN102610786B (zh) * 2011-12-20 2014-06-18 南昌大学 一种三元复合纸电池正极的制备方法
JP6115790B2 (ja) * 2014-09-18 2017-04-19 トヨタ自動車株式会社 電極ペーストの検査方法ならびに電極の製造方法
CN105140370B (zh) * 2015-10-09 2019-07-19 Tcl集团股份有限公司 Qled、qled显示屏及制备方法
GB2539297A (en) 2016-01-15 2016-12-14 Saralon Gmbh Thin battery and manufacturing method therefore
CN106469326A (zh) * 2016-08-30 2017-03-01 常州恩福赛印刷电子有限公司 一种半有源电子年检标签
CN106356539A (zh) * 2016-08-30 2017-01-25 常州恩福赛印刷电子有限公司 一种在射频识别标签天线上印刷柔性电池及其制造方法
GB2553791B (en) 2016-09-14 2019-04-24 Dst Innovations Ltd Flexible battery
US10879540B2 (en) 2017-12-04 2020-12-29 Nano And Advanced Materials Institute Limited Layered structure battery with multi-functional electrolyte
EP3680981B1 (de) * 2019-01-11 2023-03-01 VARTA Microbattery GmbH Elektrochemische zelle und anordnung elektrisch miteinander verschalteter bauteile

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US20060115717A1 (en) * 2002-02-12 2006-06-01 Schubert Mark A Flexible thin printed battery and device and method of manufacturing same
WO2008096033A1 (en) * 2007-02-06 2008-08-14 Enfucell Oy Thin battery and a method of manufacturing a thin battery

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US4595250A (en) * 1983-04-15 1986-06-17 La Telemecanique Electrique Modular apparatus for coded interconnection between electronic cards and a printed circuit board
US5495250A (en) * 1993-11-01 1996-02-27 Motorola, Inc. Battery-powered RF tags and apparatus for manufacturing the same
US6379835B1 (en) * 1999-01-12 2002-04-30 Morgan Adhesives Company Method of making a thin film battery
US20060115717A1 (en) * 2002-02-12 2006-06-01 Schubert Mark A Flexible thin printed battery and device and method of manufacturing same
WO2008096033A1 (en) * 2007-02-06 2008-08-14 Enfucell Oy Thin battery and a method of manufacturing a thin battery

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Publication number Priority date Publication date Assignee Title
US20160181952A1 (en) * 2014-12-19 2016-06-23 Samsung Electronics Co., Ltd. Energy generating device, and method of manufacturing the same
US9787221B2 (en) * 2014-12-19 2017-10-10 Samsung Electronics Co., Ltd. Energy generating device, and method of manufacturing the same

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Publication number Publication date
EP2335306A1 (en) 2011-06-22
CN102150301A (zh) 2011-08-10
CN102150310A (zh) 2011-08-10
EP2335306A4 (en) 2012-03-28
US8574742B2 (en) 2013-11-05
KR20110053256A (ko) 2011-05-19
WO2010026286A1 (en) 2010-03-11
JP2012502416A (ja) 2012-01-26
US20110165447A1 (en) 2011-07-07
WO2010026285A1 (en) 2010-03-11

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