[go: up one dir, main page]

WO1998004009A1 - Electrodes a capacite volumetrique elevee et cellules electrochimiques utilisant ces electrodes - Google Patents

Electrodes a capacite volumetrique elevee et cellules electrochimiques utilisant ces electrodes Download PDF

Info

Publication number
WO1998004009A1
WO1998004009A1 PCT/US1997/010933 US9710933W WO9804009A1 WO 1998004009 A1 WO1998004009 A1 WO 1998004009A1 US 9710933 W US9710933 W US 9710933W WO 9804009 A1 WO9804009 A1 WO 9804009A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
carbon
electrode material
density
graphite
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.)
Ceased
Application number
PCT/US1997/010933
Other languages
English (en)
Inventor
Zhenhua Mao
Dong Chen
Jinshan Zhang
Anaba A. Anani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Motorola Solutions Inc
Original Assignee
Motorola Inc
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 Motorola Inc filed Critical Motorola Inc
Publication of WO1998004009A1 publication Critical patent/WO1998004009A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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

  • This invention relates in general to the field of electrodes and electrode materials for electrochemical cells and in particular to methods of fabricating said electrodes and electrode materials.
  • Lithium batteries in general include a positive electrode fabricated of, for example, a transition metal oxide material, and a negative electrode fabricated of an activated carbon such as graphite or petroleum coke. New materials for both electrodes have been investigated intensely because of the high potential for improved energy density. To date, most of the attention has been focused on the transition metal oxide electrode.
  • Activated carbon materials are routinely prepared by using difunctional monomers as polymer precursors.
  • difunctional monomers include resins of furfuryl alcohol, phenol, formaldehyde, acetone, or furfuryl alcohol-phenol copolymers.
  • Other precursors include polyacrylonitrile, and rayon polymers, both as described in a publication to Jenkins, et al entitled "Polymeric Carbons-Carbon Fiber, Glass and Char., Cambridge University Press, Cambridge, England (1976). Materials which result from these processes are typically characterized by relatively low yields as well as high cost and/or low capacity.
  • FIG. 1 is a schematic representation of an electrochemical cell, including an electrode fabricated of an active electrode material and a lubricant material, in accordance with the instant invention.
  • FIG. 1 there is illustrated therein a schematic representation of an electrochemical cell 10, such as a battery or an electrochemical capacitor, and including an electrode fabricated of an active electrode material such as carbon, and including a lubricant material for increasing the density of an electrode fabricated therefrom in accordance with the instant invention.
  • the electrochemical cell 10 includes a positive electrode or cathode 20, and negative electrode or anode 30, and an electrolyte 40 disposed therebetween.
  • the cell negative electrode or anode 30 is fabricated of an active electrode material capable of reversible charge storage such as the carbon materials described in the aforementioned patent applications, as well as a lubricant material such as is described in greater detail hereinbelow.
  • the positive electrode 20 of the cell 10 in the case of a lithium based cell may be fabricated from a lithiated transition metal oxide such as is well known in the art.
  • the positive electrode material may be fabricated of a material such as that described in commonly assigned, co-pending U.S. Patent Application Serial No. 08/464,440 filed June 5, 1995 in the name of Mao, et al and entitled "Positive Electrode Materials for Rechargeable Electrochemical Cells and Method of Making Same," the disclosure of which is incorporated herein by reference.
  • the electrolyte 40 disposed between the electrodes may be any of the electrolytes known in the art including, for example, LiCl ⁇ 4 in propylene carbonate or a polyethylene oxide impregnated with a lithiated salt.
  • the electrolyte 40 may also act as a separator between the positive and negative electrodes.
  • the electrolyte may be aqueous, non-aqueous, solid state, gel or some combination thereof.
  • the electrolyte material may be fabricated in a manner such as that described in commonly assigned copending Patent Application Serial No. 08/518,732 filed August 24, 1995 in the name of Oliver, et al and entitled "Blended Polymer Gel Electrodes" the disclosure of which is incorporated herein by reference.
  • an electrode material capable of reversibly intercalating and deintercalating lithium ions and adapted for use as an electrode in an electrochemical cell such as that shown in FIG. 1.
  • the electrode material comprises an active electrode material and a lubricant material.
  • the active electrode material is preferably a carbon material, and is formed by the pyrolitic decomposition of a lignin material, which results in a substantially amorphous carbon material characterized by a reversible lithium capacity greater than approximately 500 milliamperes hours per gram (mAh/g) and a density of up to 1.6 grams per cubic centimeters (g/cc ⁇ ).
  • the carbon materials which result from the pyrolitic condensation of lignin materials are preferably amorphous though may be partially or completely crystalline. As the materials which result from this process are amorphous and hence relatively hard, it is difficult to pack them into a highly dense electrode structure.
  • the electrode material further comprise a lubricant material to provide the required compression attribute to the electrode structure.
  • the lubricant is a second carbon material characterized by a density of at least 1.2 times greater than that of the first carbon material.
  • the second carbon material is preferably a graphite or other activated carbon which has both a relatively high density as compared to the amorphous carbon resulting from the lignin decomposition, and is compressible along phases of its graphite sheet.
  • the first carbon material comprises between 60 and 90 wt% of the electrode material while the graphatic material comprises between 10 and 40 wt% of said electrode material.
  • the graphatic second carbon material comprises between 20 and 35 wt% of the overall electrode material.
  • the first carbon material is fabricated by the pyrolitic decomposition of lignins as described in commonly assigned copending U.S. Patent
  • Lignin is a by-product of the paper and pulp industry which can yield an amorphous carbon material with capacities in excess of 500 mAh/g, and a yield in excess of 50%. Lignin is generated at a rate of over 50 million metric tons a year, hence, using lignin as a starting material to make an amorphous carbon material for an electrode in accordance with the instant invention, provides a tremendous economic advantage. Moreover, lignin is a renewable resource and its existence in the biosphere is estimated to be 3xl ⁇ H metric tons with an annual biosynthetic rate of 2x10 ⁇ 0 tons per year.
  • Preferred lignins for use in the pyrolitic decomposition process as described in the aforementioned patent application include three cinnamyl alcohols. These alcohols are the monomeric precursors of the lignin and include p-coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol.
  • the structural units of each of the three cinnamyl alcohols have oxyphenyl propyloxy skeletons and differ from each other only in the number of methoxyl groups attached to the benzene ring. In the polymeric structure of lignin, these structural units are held together by a variety of ether and carbon/carbon bonds.
  • Amorphous carbon material is used as the active electrode material in the fabrication of a negative electrodes in accordance with the instant invention are characterized by a density on the order of up to approximately 1.6g/cm ⁇ , and a d-spacing of the (002) plane of approximately between 3.8 angstroms and 4.2 angstroms.
  • the electrode materials of the instant invention further include a relatively soft material blended with the "hard” amorphous carbon.
  • the addition of graphite as a lubricant is desirable since the density of graphite is relatively high and it is highly compressible.
  • blending operative amounts of a high density lubricant such as graphite, with the high capacity/low density carbon which results from the pyrolitic condensation of lignin results in a overall electrode material which has electrochemical properties better than either of the two materials by themselves.
  • a high density lubricant such as graphite
  • graphite is known to be an acceptable material for lithium ion intercalation and deintercalation, and its overall percentage in the mixture is relatively small, i.e., on the order of 10-40%, overall capacity of the mixture is not substantially compromised nor is it significantly lower than the carbon electrode by itself.
  • electrode density is increased substantially thereby offsetting the density losses experienced by carbon alone.
  • the lubricant has been described thus far only as graphite.
  • Graphite also serves the function of an adhesive, thus reducing the content of binder material in the overall electrode, and serving to further increase the density of the carbon electrode.
  • Table 2 shows the maximum mass ratio of cathode to anode according to the calculated capacities.
  • the cathode used has a capacity of 235 mAh/g.
  • the cathode capacity in Table 2 is the total reversible capacity per unit weight of the cathode active material.
  • Capacity C A mass ratio Cathode wt% wt% (mAh/q) (mAh/q) capacity
  • Electrodes according to the instant invention were made of different compositions by fabricating the mixtures and pressing under 500 lbs. per square inch to a width of 2.5 inches. Densities of those electrodes were calculated according to the active material loading and coating thickness. Results are listed below in Table 3.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Cette invention se rapporte à un matériau d'électrodes pour un élément accumulateur rechargeable au lithium (10) dont l'électrode négative (30) est fabriquée à partir d'une combinaison d'un premier et d'un second matériau au carbone. Le premier matériau carbone est constitué d'un matériau carbone essentiellement amorphe qui est de préférence le produit de décomposition pyrolytique d'un matériau précurseur à la lignine. Le second matériau carbone utilisé dans le matériau d'électrode négative est de préférence également un matériau carbone, bien qu'il se caractérise par une densité plus grande que celle du carbone amorphe. A cet égard, le second matériau carbone est de préférence un matériau carbone à la graphite. La présence de graphite dans la composition totale de l'électrode augmente la densité de l'électrode, agit comme liant dans le compression des matériaux de l'électrode sur un substrat porteur de courant et comme lubrifiant dans le processus de fabrication.
PCT/US1997/010933 1996-07-19 1997-07-16 Electrodes a capacite volumetrique elevee et cellules electrochimiques utilisant ces electrodes Ceased WO1998004009A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US68437296A 1996-07-19 1996-07-19
US08/684,372 1996-07-19

Publications (1)

Publication Number Publication Date
WO1998004009A1 true WO1998004009A1 (fr) 1998-01-29

Family

ID=24747772

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/010933 Ceased WO1998004009A1 (fr) 1996-07-19 1997-07-16 Electrodes a capacite volumetrique elevee et cellules electrochimiques utilisant ces electrodes

Country Status (1)

Country Link
WO (1) WO1998004009A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110518243A (zh) * 2019-08-20 2019-11-29 台州立拓能源有限公司 木质素在制备锂电池石墨负极材料中的应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE33306E (en) * 1984-05-07 1990-08-21 Sanyo Chemical Industries, Ltd. Secondary battery or cell with improved rechargeability
US5344726A (en) * 1991-06-17 1994-09-06 Sharp Kabushiki Kaisha Carbon anode for secondary battery
US5451477A (en) * 1993-06-03 1995-09-19 Sony Corporation Non-aqueous liquid electrolyte secondary battery
US5529859A (en) * 1994-04-15 1996-06-25 National Research Council Of Canada Elecrolyte for a secondary cell
US5543021A (en) * 1994-09-01 1996-08-06 Le Carbone Lorraine Negative electrode based on pre-lithiated carbonaceous material for a rechargeable electrochemical lithium generator
US5589289A (en) * 1995-09-27 1996-12-31 Motorola, Inc. Carbon electrode materials for electrochemical cells and method of making same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE33306E (en) * 1984-05-07 1990-08-21 Sanyo Chemical Industries, Ltd. Secondary battery or cell with improved rechargeability
US5344726A (en) * 1991-06-17 1994-09-06 Sharp Kabushiki Kaisha Carbon anode for secondary battery
US5451477A (en) * 1993-06-03 1995-09-19 Sony Corporation Non-aqueous liquid electrolyte secondary battery
US5529859A (en) * 1994-04-15 1996-06-25 National Research Council Of Canada Elecrolyte for a secondary cell
US5543021A (en) * 1994-09-01 1996-08-06 Le Carbone Lorraine Negative electrode based on pre-lithiated carbonaceous material for a rechargeable electrochemical lithium generator
US5589289A (en) * 1995-09-27 1996-12-31 Motorola, Inc. Carbon electrode materials for electrochemical cells and method of making same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110518243A (zh) * 2019-08-20 2019-11-29 台州立拓能源有限公司 木质素在制备锂电池石墨负极材料中的应用
CN110518243B (zh) * 2019-08-20 2021-03-23 台州立拓能源有限公司 木质素在制备锂电池石墨负极材料中的应用

Similar Documents

Publication Publication Date Title
US20230231119A1 (en) Prelithiated And Methods For Prelithiating An Energy Storage Device
US10608247B2 (en) Negative electrode for secondary battery, method of fabricating the same and secondary battery including the same
US20230282836A1 (en) Lithium metal negative electrode plate, electrochemical apparatus, and electronic device
JP4137350B2 (ja) リチウム二次電池用の負極材料及びリチウム二次電池用の電極及びリチウム二次電池並びにリチウム二次電池用の負極材料の製造方法
US5635151A (en) Carbon electrode materials for lithium battery cells and method of making same
US8465874B2 (en) Lithium-ion secondary battery and manufacturing method thereof
US20230307618A1 (en) Lithium metal negative electrode plate, electrochemical apparatus, and electronic device
KR100544986B1 (ko) 유기 전해질 전지
EP2056379B1 (fr) Électrode négative pour batterie au lithium rechargeable et batterie au lithium rechargeable l'incluant
US20230231100A1 (en) Electrochemical devices, electronic devices
WO2025209064A1 (fr) Matériau d'électrode positive, dispositif électrochimique et dispositif électronique
US20220271341A1 (en) Electrolyte, and electrochemical apparatus and electronic apparatus including same
JP4900994B2 (ja) 非水電解質二次電池
US11909058B2 (en) Method and system for formation of cylindrical and prismatic can cells
JP2001307735A (ja) リチウム二次電池
JP2002042785A (ja) リチウム電池
KR101491805B1 (ko) 전극조립체 및 이를 구비하는 리튬 이차 전지
JP3475530B2 (ja) 非水電解質二次電池
WO1998004009A1 (fr) Electrodes a capacite volumetrique elevee et cellules electrochimiques utilisant ces electrodes
KR100855802B1 (ko) 2차 전지용 음극재 및 이를 이용한 2차 전지
JPH10106546A (ja) 電池用電極の製造方法
JP2005222829A (ja) 電解質および電池
JPH11307100A (ja) 有機電解質電池
JP3775022B2 (ja) ゲル状電解質及びゲル状電解質電池
JP2000251888A (ja) リチウム電池

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP KR

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 98506931

Format of ref document f/p: F