WO2023012812A1 - Collecteur de courant d'anode à base de titane - Google Patents

Collecteur de courant d'anode à base de titane Download PDF

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Publication number
WO2023012812A1
WO2023012812A1 PCT/IN2022/050463 IN2022050463W WO2023012812A1 WO 2023012812 A1 WO2023012812 A1 WO 2023012812A1 IN 2022050463 W IN2022050463 W IN 2022050463W WO 2023012812 A1 WO2023012812 A1 WO 2023012812A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium
current collector
foil
titanium oxide
anode current
Prior art date
Application number
PCT/IN2022/050463
Other languages
English (en)
Inventor
Gopinath SH
Nileshwar Pramila Rao
Datta Rajaram Sagare
Original Assignee
Tvs Motor Company Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tvs Motor Company Limited filed Critical Tvs Motor Company Limited
Publication of WO2023012812A1 publication Critical patent/WO2023012812A1/fr

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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/75—Wires, rods or strips
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • a power unit such as battery
  • the power unit is a storage device that stores and converts chemical energy into electrical energy by electrochemical reaction.
  • the power unit for example a Lithium-ion (Li-ion) battery, can be used to power various devices, such as electronic devices, power tools, and automobiles.
  • the power unit delivers electrical energy as a result of flow of electrons between the negative terminal and the positive terminal of the battery.
  • the power unit may be disposable after use or can be rechargeable.
  • FIG. 1 illustrates a method for fabricating a titanium-based anode current collector for a power unit, according to an aspect of the present subject matter.
  • FIG. 2 illustrates a system for performing the anodization process of a Titanium foil for making a titanium-based anode current collector, according to an aspect of the present subject matter.
  • FIG. 3 illustrates a microscopic view of the titanium-based anode current collector having a fire-retardant material electrodeposited thereon, according to another aspect of the present subject matter.
  • the power unit usually, includes a casing in which the components of the power unit are disposed.
  • the casing can have an electrolyte, and a cathode and an anode disposed in the electrolyte, usually, at two opposite ends of the casing.
  • the power unit further includes two current collectors, a cathode current collector and an anode current collector.
  • the cathode current collector is attached to the cathode
  • the anode current collector is attached to the anode.
  • the electrolyte carries positively charged ions from the anode to the cathode and vice- versa through the separator. The movement of ions create a charge at the current collectors, resulting in a flow of electric current between the current collectors.
  • Aluminium (Al) foils and Copper foils (Cu) are generally used as the cathode current collector and the anode current collector, respectively.
  • Power units such as rechargeable power units including Li- ion batteries
  • Li-ion batteries have various safety concerns.
  • the Li-ion battery is short-circuited or exposed to high temperatures, exothermic reactions can be triggered leading to thermal runaway which can cause permanent damage to the power unit due to fire. Therefore, fire-retardant materials which activate at a high temperature are used to prevent such fire-related accidents in the power units.
  • the fire-retardant material is usually embedded into the two current collectors to enhance safety of the power unit. Therefore, the current collectors should be able to hold the fire-retardant material.
  • the current collectors might not be able to firmly hold the fire-retardant material over time.
  • Examples of a power unit are provided which can be used for providing electrical energy to an external device.
  • the power unit employs a titanium-based (Ti- based) anode current collector.
  • a titanium (Ti) foil can be anodized to form titanium oxide tubes having a nano-tubular structure.
  • the titanium oxide tubes are used as the anode current collector and provides an enhanced holding capacity of a fire- retardant material.
  • the Ti-based anode current collector is fabricated from the Ti foil and is used in a power unit.
  • the Ti foil is first modified into a predetermined shape and used in a setup where, the Ti foil acts as an anode and the noble metal acts as a cathode.
  • the Ti foil and the noble metal are disposed into an electrolyte and are electrically connected to one another by a potentiostat.
  • the electrolyte may be a fluoride-based electrolyte or an ethylene glycol- based electrolyte.
  • varying voltages are applied for a predetermined time across the Ti anode and the noble metal cathode by the potentiostat for electrochemically anodizing the Ti foil.
  • the electrochemical anodization can cause the Ti foils to be formed into titanium oxide tubes having a predetermined aspect ratio.
  • the titanium oxide tubes as the name suggests, have a nano-tubular structure and can be used as the anode current collector in the power unit, such as a Lithium-ion (Li-ion) battery.
  • the Ti-based current collector may be embedded with the fire-retardant material, such as a triphenyl phosphate (TPP) additive.
  • TPP triphenyl phosphate
  • the TPP additive is electrodeposited on the Ti-based anode current collector.
  • the electrodeposition of the TPP additive is done using a three-electrode system.
  • the Ti-based anode current collector titanium oxide tubes
  • a platinum-based material is used as counter electrode
  • a silver-based material is used as reference electrode.
  • the TPP additive is mixed with trimethyl phosphate (TMP), and the composite resulting thereafter is electrodeposited on the titanium oxide tubes. Being a liquid solvent, TMP enables a better electrodeposition on the titanium oxide tubes.
  • TMP trimethyl phosphate
  • the nano-tubular structure of the Ti-based anode current collector can increase the holding capacity of the current collector for holding the fire- retardant material thereon.
  • the titanium oxide tube formed by anodizing Ti foil is used as the anode current collector for the power unit.
  • the power unit can be a Lithium-ion (Li-ion) battery.
  • the power unit includes a casing having an electrolyte and two electrodes.
  • the first electrode is a cathode disposed in the electrolyte at one end of the casing.
  • the second electrode is an anode disposed in the electrolyte at another end of the casing.
  • the cathode and the anode are disposed in the electrolyte at opposing ends of the casing.
  • the cathode is attached to an aluminium-based cathode current collector, where the aluminium- based cathode current collector is electrochemically anodized to form alumina tubes. Further, the anode is attached to a titanium-based anode current collector, where the titanium-based anode current collector is electrochemically anodized to form titanium oxide tubes.
  • the alumina tubes and the titanium oxide tubes have pores or nano-tubular structure.
  • the titanium-based anode current collector and the aluminium-based cathode current collector are electrodeposited with the fire-retardant material, such as a triphenyl phosphate (TPP) additive.
  • TPP triphenyl phosphate
  • FIG. 1 illustrates a method 100 for fabricating a titanium- based anode current collector for a power unit, according to an aspect of the present subject matter.
  • a titanium (Ti) foil is electrochemically anodized.
  • the Ti foil Before, the anodization process, the Ti foil may have to be pretreated.
  • Block 102 refers to the pre-treatment process of Ti foil.
  • the Ti foil may be pretreated at several levels before the process of anodization. Initially, the Ti foil may be pickled with oxalic acid. In an example, for pickling the Ti foil, a 2M oxalic acid solution may be used. Further, the Ti foil may be pickled for 30 minutes at a temperature of 60 degrees with 2M oxalic acid solution.
  • the Ti foil may be sonicated separately with acetone, isopropanol and Millipore water.
  • the Ti foil may be sonicated with each of the solutions separately for 15 minutes each. Later, the Ti foil may be kept separately and may be left out for drying. In an example, the Ti foil may be kept overnight for drying. As a result, the Ti foil is prepared for the anodization process.
  • the Ti foil is modified into a predetermined shape and size.
  • the Ti foil can be cut to form a plurality of “L” shape pieces, each having a dimension of 1 cm x 1 cm and thickness of 100 microns.
  • the Ti foil may be used as an anode or working electrode for the anodization process.
  • a noble metal may be used as cathode or counter electrode for the anodization process.
  • platinum (Pt) mesh having a dimension of 2.5 cm x 2.5 cm may be used as the cathode for the anodization process.
  • the anode i.e., the Ti foil and the cathode, i.e., the noble metal
  • the electrolyte solution may be a fluoride-based electrolyte or an ethylene glycol-based electrolyte.
  • the electrolyte may be a mixture of 94.5 % ethylene glycol by weight, 5 % water by weight and 0.5 % ammonium fluoride by weight.
  • the anode i.e., the Ti foil and the cathode, i.e., the noble metal, are electrically connected to each other through a potentiostat.
  • the potentiostat may apply varying voltages for a predetermined time for electrochemically anodizing the Ti foil. For example, the potentiostat may apply different voltages for a duration of 1 hour. Due to the anodization process, the Ti foil is formed into titanium oxide tubes having a predetermined aspect ratio.
  • the aspect ratio of the titanium oxide tubes may be a ratio of the mean length of the titanium oxide tubes and the mean diameter of the titanium dioxide tubed.
  • the titanium oxide tubes formed from the Ti foil may have an aspect ratio between 30 to 50.
  • the titanium oxide tube may undergo a posttreatment process after the anodization process.
  • the post-treatment process includes sonicating the titanium oxide tubes in Millipore water.
  • the titanium oxide tubes may be sonicated in Millipore water for 5 minutes.
  • the titanium oxide tubes may then be kept separately and left out for drying. In an example, the titanium oxide tubes may be kept overnight for drying.
  • a fire-retardant material such as triphenyl phosphate (TPP) additive is electrodeposited on the titanium oxide tubes to be used as anode current collector for the power unit.
  • TPP triphenyl phosphate
  • the electrodeposition of the TPP additive is done using a three-electrode system.
  • the titanium oxide tubes may be a working electrode, a plurality of platinum-based materials may be used as a counter electrode, and a silver-based material may be used as reference electrode.
  • platinum mesh may be used as counter electrode and, silver foil or silver chloride (AgCI) may be used a reference electrode.
  • the titanium oxide tubes working electrode, platinum-based material counter electrode and the silver-based material reference electrode may be deposited in an electrolyte solution.
  • the electrolyte solution may include TPP and TMP mixed in Millipore water.
  • the working electrode, the counter electrode and the reference electrode may be electrically connected, for example, using the potentiostat. Further, the potentiostat applies a voltage, and upon application of the voltage, exchange of ions may occur between the titanium oxide tubes working electrode and the platinum-based material counter electrode.
  • Table 1 refers to diameter of the titanium oxide tubes which may be achieved, based on different anodization times.
  • Table 1 It is apparent from Table 1 that the diameter of the titanium oxide tubes increases as the duration of the anodization process, i.e., anodization time, increases.
  • Table 2 refers to diameter and wall thickness of titanium oxide tubes (TNT) based on voltage applied by the potentiostat.
  • FIG. 2 illustrates a system 200 for performing the anodization process of the Titanium foil for making a titanium-based anode current collector, according to an aspect of the present subject matter.
  • the system 200 may perform the method 100, as explained above with reference to FIG.1.
  • the system 200 may include an electrolyte 206 and a potentiostat 208.
  • the electrolyte 206 may have an anode 202 and a cathode 204 disposed in it.
  • the Ti foil maybe used as anode 202 or working electrode.
  • the cathode 204 or counter electrode may be a noble metal, such as platinum.
  • the electrolyte 206 may be a fluoride-based electrolyte or an ethylene glycol-based electrolyte.
  • the potentiostat 208 may be adapted to electrically connect the anode 202 and the cathode 204 disposed in the electrolyte 206.
  • the potentiostat 208 may apply varying voltages for a predetermined time for electrochemically anodizing the Ti foil.
  • the Ti foil may be anodized to form titanium oxide nanotubes.
  • the titanium oxide nanotubes may be used as an anode current collector in the power unit.
  • the size of the titanium oxide tubes varies based on different parameters. For instance, the diameter and wall thickness of the titanium oxide tube may be dependent on the anodization time and anodization voltage, i.e., voltage applied by the potentiostat, as described above.
  • FIG. 3 illustrates a microscopic view of the titanium oxide tubes anode current collector 300 having a fire-retardant material electrodeposited thereon, in accordance with an example of the present subject matter.
  • the fire-retardant material may be the triphenyl phosphate (TPP) additive, where TPP is a solid solvent and has a high voltage threshold, of approximately 4.9 volts.
  • TPP triphenyl phosphate
  • the power unit having the anode current collector as the titanium oxide tubes which when embedded with TPP provides a stable operation of the power unit even in high voltage operating conditions.
  • solid solvents might not be easily electrodeposited on the titanium oxide tubes anode current collector.
  • trimethyl phosphate may be used as fire-retardant material, which is a liquid solvent and can be electrodeposited on the titanium oxide tubes anode current collector with relative ease.
  • TMP has a lower voltage threshold. Therefore, operation of power unit may not be stable for high voltage operating conditions. For instance, TMP has a voltage threshold level of approximately 4.2 volts.
  • the titanium oxide tubes can be used as anode current collector for the power unit.
  • the power unit (not shown in Fig. 3) has the titanium-based anode current collector.
  • the power unit may be a Lithium-ion (Li-ion) battery used for generating power for mobile phones, laptops, desktops, electrical vehicle, and the like.
  • the power unit includes a casing (not shown in Fig. 3) having the electrolyte (not shown in Fig. 3), a separator (not shown in Fig. 3), and two electrodes (not shown in Fig. 3).
  • the electrolyte in case of a Li-ion battery, can be Lithium salts with organic solvents, such as (LiPF6) in Ethylene Carbonate or Ethyl Methyl Carbonate.
  • the separator is disposed in the electrolyte to separate the two electrodes.
  • the separator in case of a Li-ion battery, can be a polymer.
  • the first electrode is the cathode disposed in the electrolyte at one end of the casing.
  • the cathode in case of a Li-ion battery, can be one of LiCoO2 (LCO), LiMn 2 O4 (LMO), LiFePC (LFP), and LiNiMnCoO 2 (NMC).
  • the second electrode is the anode disposed in the electrolyte at another end of the casing.
  • the anode in case of a Li-ion battery, can be a graphite and silicon.
  • the cathode and the anode are disposed in the electrolyte at opposing ends of the casing.
  • the cathode is attached to an aluminium-based cathode current collector, where the aluminium-based cathode current collector is electrochemically anodized to form alumina tubes. Further, the anode is attached to a titanium-based anode current collector, where the titanium-based anode current collector is electrochemically anodized to form titanium oxide tubes.
  • the alumina tubes and the titanium oxide tubes have pores or nano-tubular structure.
  • the alumina tubes are formed by electrochemically anodizing aluminium foils having a thickness of approximately 50-100 microns.
  • the titanium oxide tubes may be formed by electrochemically anodizing Ti foils having a thickness of 50- 100 microns.
  • the alumina tubes and the titanium tubes may have an approximate thickness of 15-25 nanometers.
  • a fire-retardant material is electrodeposited on the alumina tubes and the titanium oxide tubes.
  • the fire-retardant material may be a composite of TPP and TMP.
  • the composite will have advantages of both TPP and TMP, such as a high voltage threshold due to TPP, and better electrodeposition ability due to TMP.
  • a thickness of 1 to 2 microns of fire-retardant material is electrodeposited on the current collectors.
  • the current collectors Owing to the nano-tubular structure for current collectors, i.e., alumina tubes as cathode current collectors as well as for the titanium oxide tubes as anode current collectors, the current collectors have a better ability to firmly hold the fire-retardant material. Therefore, the fire- retardant material can be effectively used for a longer period of time. Accordingly, the power unit can have a longer life due to enhanced protection in high temperature situations, such as thermal runaway.
  • titanium-based anode current collector and the method of fabrication thereof have been described in language specific to structural features and/or methods, it is to be understood that the appended claims are not limited to the specific features described. Rather, the specific features are disclosed as examples of the titanium-based anode current collector and the method of fabrication thereof.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

Des exemples d'un collecteur de courant d'anode à base de titane (Ti) sont prévus. Dans un exemple, le collecteur de courant d'anode à base de Ti est fabriqué à partir d'une feuille de Ti. La feuille de Ti et un métal noble sont modifiés selon une forme prédéterminée. La feuille de Ti sert d'anode (202) et le métal noble sert de cathode (204). La feuille de Ti et le métal noble sont disposés dans un électrolyte (206). La feuille de Ti et le métal noble sont électriquement reliés entre eux par un potentiostat (208). En outre, des tensions variables sont appliquées pendant une durée prédéterminée par le potentiostat (208) aux fins de l'anodisation électrochimique de la feuille de Ti. À la suite de l'anodisation électrochimique, les feuilles de Ti sont formées en tubes d'oxyde de titane présentant un facteur de forme prédéterminé. Les tubes d'oxyde de titane présentent une structure nano-tubulaire et sont utilisés en tant que collecteur de courant d'anode dans une unité d'alimentation.
PCT/IN2022/050463 2021-08-06 2022-05-12 Collecteur de courant d'anode à base de titane WO2023012812A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN202141035682 2021-08-06
IN202141035682 2021-08-06

Publications (1)

Publication Number Publication Date
WO2023012812A1 true WO2023012812A1 (fr) 2023-02-09

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PCT/IN2022/050463 WO2023012812A1 (fr) 2021-08-06 2022-05-12 Collecteur de courant d'anode à base de titane

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030118909A1 (en) * 2001-11-14 2003-06-26 Paulot William M. Carbon-coated titanium current collectors for use in alkali metal electrochemical cells
US7005214B2 (en) * 2001-11-02 2006-02-28 Wilson Greatbatch Technologies, Inc. Noble metals coated on titanium current collectors for use in nonaqueous Li/CFx cells
US9905849B2 (en) * 2012-04-18 2018-02-27 Lg Chem, Ltd. Electrode assembly and lithium secondary battery including the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7005214B2 (en) * 2001-11-02 2006-02-28 Wilson Greatbatch Technologies, Inc. Noble metals coated on titanium current collectors for use in nonaqueous Li/CFx cells
US20030118909A1 (en) * 2001-11-14 2003-06-26 Paulot William M. Carbon-coated titanium current collectors for use in alkali metal electrochemical cells
US9905849B2 (en) * 2012-04-18 2018-02-27 Lg Chem, Ltd. Electrode assembly and lithium secondary battery including the same

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