WO2008037154A1 - Accumulateur lithium-ion secondaire utilisant du métal en mousse en tant que collecteur de courant et ensemble d'accumulateur l'utilisant - Google Patents

Accumulateur lithium-ion secondaire utilisant du métal en mousse en tant que collecteur de courant et ensemble d'accumulateur l'utilisant Download PDF

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Publication number
WO2008037154A1
WO2008037154A1 PCT/CN2007/001285 CN2007001285W WO2008037154A1 WO 2008037154 A1 WO2008037154 A1 WO 2008037154A1 CN 2007001285 W CN2007001285 W CN 2007001285W WO 2008037154 A1 WO2008037154 A1 WO 2008037154A1
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WO
WIPO (PCT)
Prior art keywords
lithium ion
current collector
battery
ion battery
foam
Prior art date
Application number
PCT/CN2007/001285
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English (en)
Chinese (zh)
Inventor
Xiaoping Ren
Jie Sun
Original Assignee
Xiaoping Ren
Jie Sun
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 Xiaoping Ren, Jie Sun filed Critical Xiaoping Ren
Publication of WO2008037154A1 publication Critical patent/WO2008037154A1/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
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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

  • Lithium-ion battery or battery pack Lithium-ion battery or battery pack
  • the present invention relates to a secondary lithium ion battery or battery pack using a current collector made of a metal foam.
  • a current collector made of a metal foam.
  • the positive electrode current collector is foamed aluminum
  • the negative electrode current collector is foamed copper, nickel foam or foamed iron.
  • the present invention also relates to a secondary lithium ion battery pack composed of the above single lithium ion battery.
  • the present invention generally relates to lithium ion batteries.
  • lithium ion batteries At present, as the market demands for the performance of lithium ion batteries continue to increase, users demand higher energy density and higher current discharge performance of lithium ion batteries.
  • Each lithium-ion battery manufacturer has continuously researched and developed the above-mentioned customer requirements to increase the energy density of the battery by increasing the utilization of the effective space of the battery; more effectively exerting the electrochemical activity of the active material of the battery to improve its effective utilization.
  • the fundamental improvement in the energy density and electrochemical performance of lithium-ion batteries is to develop new positive and negative materials that can be used in lithium-ion batteries with higher energy density.
  • the second is how to reduce the space in which the battery is ineffective, to increase the filling amount of the active material (positive and negative electrode materials), or to take appropriate physical or chemical methods to increase the utilization rate of the active material.
  • the following methods can be used: a thinner current collector and a membrane are used; more effective additives are used to increase the effective utilization of the active material.
  • the metal foam comprises a foamed alloy.
  • foam metal is used instead of the conventional foil current collector to increase the capacity and rate discharge of the lithium ion battery.
  • the reason for the performance can be presumed as follows. Since the three-dimensional pores of the high porosity are present in the metal foam, the active material can be filled in the pores instead of being coated on the surface like the foil current collector. After the high porosity three-dimensional pores in the metal foam, not only the filling rate is increased, but also the three-dimensional pore structure and high porosity of the foam metal are more favorable for the uniform distribution of the current density and the electrolyte penetration and uniform distribution. Thereby, the utilization ratio of the active material of the lithium ion battery can be improved, and the capacity and rate discharge performance of the lithium ion battery can be improved.
  • the active material can only be distributed on the surface of the current collector.
  • the electrical energy converted into chemical energy is mainly transmitted to the active material by the current collector (that is, the active material converts the electrical energy into chemical energy during the charging process, and the process is an energy input process; the use process is a discharge process, and the chemical energy is converted into electrical energy by discharge. This process is the energy output process.)
  • the active shield near the current collector and the active material away from the current collector vary greatly in the distribution of electrical energy. The closer to the current collector, the more energy is distributed and the more uniform. The farther away from the current collector, the less energy it distributes.
  • the metal foil used in the current collector of the ionic battery causes the input and output of the active material of the ionic battery and the unevenness of the energy during the conversion process, which affects the utilization of the active material.
  • the inventors have conducted extensive experiments to improve the current collector of a lithium ion battery, and improve the energy density and rate discharge performance of the lithium ion battery by the improvement of the current collector. This is also a primary goal to be achieved by the present invention.
  • the lithium ion battery fabricated by the present scheme includes the following parts: an electrode, an electrolyte, a separator, and a container.
  • the electrode includes a positive electrode and a negative electrode, the positive electrode includes a positive electrode current collector and a positive electrode active material; the negative electrode includes a negative electrode current collector and a negative electrode active material; the separator may be a simple solid insulating layer, a gel material, or a conductive property.
  • the container is a container of a positive electrode, a negative electrode, a separator, and an electrolyte, and may be a container having a fixed shape or a container made of a film material.
  • At least one of the cathode current collector and the anode current collector in the secondary lithium ion battery includes a metal foam, for example, the cathode current collector is aluminum foam, and the anode current collector is foam copper or foam iron. Or foamed nickel.
  • At least one of the cathode current collector and the anode current collector in the secondary lithium ion battery may include a foam alloy, for example, the cathode current collector is a foam aluminum alloy, and the anode current collector is foam copper. Alloy or foamed iron alloy or foamed nickel alloy. As is known to those skilled in the art, “aluminum alloy” generally refers to any alloy in which the single largest component of the alloy composition is aluminum. Similarly, “copper alloy”, “iron alloy” and “nickel alloy” refer to any alloy in which the single largest component of the alloy is copper, iron and nickel, respectively.
  • the current density and the electrolyte in the battery can be uniformly distributed, the utilization space of the active material in the battery can be improved, and the energy density of the battery and the rate discharge performance of the battery can be improved.
  • the present invention provides secondary ionic batteries and batteries having higher energy density and better rate discharge performance.
  • lithium ion battery or battery pack is The invention can be applied to a lithium ion single cell as well as a single lithium ion battery including a protection circuit, and can also be applied to a battery pack including a plurality of single lithium ion batteries, and can also be applied to multiple batteries.
  • a battery pack of a single lithium ion battery and a protection circuit is sometimes collectively referred to as a "lithium ion battery” for the sake of simplicity.
  • the term “current collector” in the present invention means a conductive material which is in contact with the positive and negative electrode materials and is capable of current transfer, such as a metal material.
  • the present invention provides a novel secondary lithium ion battery or battery pack having higher energy density and better rate discharge performance.
  • the positive current collector of the single-cell lithium ion battery is aluminum foam, and the negative current collector is foamed copper or foamed iron or nickel foam.
  • the secondary lithium ion battery includes at least one of the above current collectors.
  • the present invention provides a secondary lithium ion battery or battery.
  • the positive current collector of the monomer lithium ion battery is a foamed aluminum alloy
  • the negative current collector is a foamed copper alloy or a foamed iron alloy or a foamed nickel alloy.
  • the secondary lithium ion battery includes at least one of the above current collectors.
  • the present invention provides a secondary lithium ion battery or battery.
  • the cathode current collector of the single-cell lithium ion battery is foamed aluminum, and the anode current collector is foamed copper alloy or foamed iron alloy or foamed nickel alloy; or, the cathode current collector of the single-cell lithium ion battery is foam aluminum alloy, and the anode current collector is foam copper. Or foamed iron or foamed nickel.
  • the secondary lithium ion battery or battery pack suitable for use in the method of the present invention is more specifically described below in a non-limiting manner.
  • the general structure of a secondary lithium ion battery includes: a positive electrode, a negative electrode, a nonaqueous electrolyte, a separator, and a container.
  • the nonaqueous electrolyte is obtained by dissolving a lithium-containing metal lithium salt such as LiPF 6 as an electrolyte in a nonaqueous solvent such as ethylene carbonate or dimethyl carbonate.
  • the separator is insoluble in the above nonaqueous solvent, and is a porous film made of, for example, polyethylene or polypropylene resin. Or, it can be The aqueous electrolyte solution plasticizes the polymeric material to obtain a solid electrolyte containing a gel electrolyte type.
  • the positive electrode preparation can be, for example, a slurry prepared by mixing a positive electrode active material, a conductive agent, and a binder in a suitable solvent, or the slurry is filled in a current collector by a slurry or the like, followed by drying and pressing into an electrode. .
  • the positive electrode active material of the battery is a compound containing a lithium element.
  • cobalt acid i.e., lithium cobalt composite oxide
  • the practice of the present invention does not depend on the characteristics of the lithium-containing composite oxide. It can be widely applied to various positive electrode active materials. Their common feature is that lithium ions can be extracted and embedded.
  • the present invention is also applicable to a lithium ion battery having various doped lithium-containing elements as a positive electrode active shield, such as a positive electrode active material including various oxides and sulfides, and examples thereof include, for example, lithium cobalt composite oxide , lithium manganese composite oxide, lithium nickel composite oxide, lithium nickel cobalt composite oxide, lithium manganese cobalt composite oxide, lithium nickel manganese cobalt composite oxide and vanadium oxide.
  • a lithium cobalt composite oxide for example, LiCo0 2
  • a lithium manganese composite oxide for example, LiMn 2 0 4
  • a lithium nickel composite oxide for example, LiNi0 2
  • lithium are preferably used.
  • a nickel-cobalt composite oxide for example, LiN — x Co x 0 2
  • a lithium manganese cobalt composite oxide for example, LiMnXc— x 0 2
  • lithium nickel manganese cobaltate and lithium iron phosphate can also be used.
  • a known conductive agent and a binder can be used in the present invention.
  • a mixing ratio of each component in the positive electrode active material can be a known ratio range.
  • the separator used in the present invention may be a known separator, and is not particularly limited.
  • it may be a type made of a synthetic resin nonwoven fabric, a polyethylene porous film or a polypropylene porous film, and a material compounded from such materials.
  • the preparation of the negative electrode can be carried out, for example, by slurrying or the like by mixing the negative electrode active material, the conductive agent and the binder in a suitable solvent, and then filling it in a current collector, followed by drying and pressing into an electrode.
  • the negative electrode active material of the battery in the present invention is a carbon-based and non-carbon-based substance in which lithium ions can be inserted and extracted, and includes, for example, a lithium alloy (for example, Liji 5 0 12 ), a metal oxide (for example, an amorphous tin). Oxide, W0 2 and MoO 2 ), TiS 2 and carbon compounds capable of intercalating and deintercalating lithium ions. It is particularly desirable to use a carbon system as the negative electrode active material.
  • the carbonaceous compounds used in the present invention include, for example, graphite, non-oriented graphite, coke, carbon fiber, spherical carbon, resin sintered carbon, and vapor-grown carbon, carbon nanotubes. Since a negative electrode comprising a specific carbon fiber or spherical carbon as described above exhibits high charging efficiency, it is particularly desirable to use mesophase pitch-based carbon fiber or mesophase pitch-based spherical carbon as a carbonaceous material.
  • the mesophase pitch-based carbon fiber and the mesophase pitch-based spherical carbon can be obtained by a known method.
  • the non-aqueous electrolyte and the outer casing may be of a known type and material, and are not particularly limited.
  • a non-aqueous electrolyte for example, a liquid non-aqueous electrolyte prepared by dissolving an electrolyte in a non-aqueous solvent, a polymer, and a non-aqueous solvent may be used.
  • a colloidal nonaqueous electrolyte prepared by compounding with a solute, a polymer solid nonaqueous electrolyte, or the like.
  • the structure of the battery may be formed by winding or lamination, and may be formed into a shape such as a column shape, a square shape or the like.
  • the current collector used in the embodiments of the present invention is a metal foam, preferably the positive electrode is aluminum foam and/or the negative electrode is foamed copper or foamed nickel or foamed iron; or, preferably, the positive electrode is a foamed aluminum alloy and/or the negative electrode is a foamed copper alloy or Foam nickel alloy or foamed iron alloy.
  • the metal foam can be obtained by a known method.
  • the preparation of metal foam has a foaming method and Electroplating method, for example:
  • the former can obtain a foamed metal by adding a foaming agent to the molten metal; the latter can deposit the metal on the polyurethane foam skeleton by an electrodeposition process, and form a foam after burning the plastic skeleton. metal.
  • Example 1 The above materials are available from domestic manufacturers such as Changsha Liyuan New Materials Co., Ltd. Of course, other conductive foam structures can also be used in the present invention.
  • the charge and discharge operation of the battery can be carried out in a manner well known in the art.
  • the single lithium ion battery used in the process is as follows: foamed copper is used as the current collector of the negative electrode, and aluminum foam is used as the current collector of the positive electrode.
  • foamed copper is used as the current collector of the negative electrode
  • aluminum foam is used as the current collector of the positive electrode.
  • a comparative example uses copper foil as the negative current collector
  • Aluminum foil is used as a positive electrode current collector.
  • Lithium cobaltate is used as a positive electrode active material
  • MCMB is used as a negative electrode active material.
  • the battery model is square 063048A. Lithium cobaltate was mixed with 7% of the binder PVDF and 5% of the conductive carbon black, and added to N-methylpyrrolidone in a ratio of 1:1 to prepare a positive electrode slurry.
  • the negative electrode material can be directly with 10.
  • the binder PVDF is mixed and added in a ratio of 1:1 to prepare a negative electrode slurry.
  • the positive electrode slurry which has been stirred and stirred is filled in the positive electrode current collector by a slurry method, and the negative electrode slurry which is uniformly stirred is filled in the negative electrode current collector by a slurry method.
  • the positive electrode current collector is made of aluminum foil
  • the negative electrode current collector is made of copper foil
  • the positive and negative electrode pastes are coated on the surface of the positive and negative electrode current collectors respectively by coating.
  • the battery container material can be aluminum shell.
  • the diaphragm is a PP material.
  • the battery case and the battery cover are welded together by laser welding.
  • the liquid is injected in an environment with a relative humidity of less than 1.5%.
  • a plurality of lithium ion batteries of a 063048 square type were produced as described above, and the positive electrode current collector used was a general-purpose aluminum foil, and the negative electrode was a commonly known copper foil.
  • the arithmetic average of the above batteries shows that the capacity of the battery 0. 2C5A is 873 ⁇ , and the capacity of 1C5A is 795 mAh.
  • a plurality of lithium ion batteries of 063048 square type are prepared, wherein the positive current collector used is aluminum foam and the negative electrode is copper foil, and the arithmetic average result of the battery shows that the battery has a capacity of 0.25 ⁇ , 1 C5A.
  • the capacity is 901 ⁇ .
  • a plurality of lithium ion batteries of 063048 square type were prepared, the positive current collector used was aluminum foil, and the negative electrode was foamed copper.
  • the arithmetic average result of the above battery showed that the capacity of the battery was 0.25 ampere, and the capacity of 1 C5A was 1 915 ampere. For 896 ⁇ ⁇ .
  • a plurality of lithium ion batteries of 063048 square type were prepared, the positive current collector used was aluminum foil, and the negative electrode was foamed nickel.
  • the arithmetic average result of the above battery showed that the volume of the battery was 0.2 ⁇ ,, the capacity of 1 C5A was It is 890 baht.
  • a plurality of lithium ion batteries of 063048 square type were prepared, the positive current collector used was aluminum foil, and the negative electrode was foamed iron.
  • the arithmetic average result of the above battery showed that the volume of the battery was 0.25 ampere, and the capacity of 1 C5A was 906 ampere. It is 887 mAh.
  • the above embodiment shows that by using the method of the present invention, the current collector of a lithium ion battery can be replaced with a metal foam material to improve the capacity and rate discharge performance of the lithium ion battery. It adapts to the current market demand for secondary lithium-ion battery capacity and rate discharge performance, has very significant commercial value, and also contributes to the basic theoretical research of lithium-ion batteries.

Abstract

L'invention concerne un accumulateur lithium-ion secondaire et un ensemble d'accumulateur; dans cet accumulateur, on utilise de l'aluminium en mousse en tant que collecteur de courant de l'électrode positive et/ou du cuivre en mousse ou du nickel en mousse en tant que collecteur de courant de l'électrode négative.
PCT/CN2007/001285 2006-09-22 2007-04-19 Accumulateur lithium-ion secondaire utilisant du métal en mousse en tant que collecteur de courant et ensemble d'accumulateur l'utilisant WO2008037154A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200610154100.5 2006-09-22
CNA2006101541005A CN1921190A (zh) 2006-09-22 2006-09-22 采用泡沫金属作为集流体的二次锂离子电池或电池组

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Publication Number Publication Date
WO2008037154A1 true WO2008037154A1 (fr) 2008-04-03

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PCT/CN2007/001285 WO2008037154A1 (fr) 2006-09-22 2007-04-19 Accumulateur lithium-ion secondaire utilisant du métal en mousse en tant que collecteur de courant et ensemble d'accumulateur l'utilisant

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US20180183040A1 (en) * 2015-09-02 2018-06-28 The Regents Of The University Of Michigan Electrochemical device including three-dimensional electrode substrate
CN114883575A (zh) * 2022-05-09 2022-08-09 清华大学 锂离子电池及其制备方法

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CN101222047B (zh) * 2008-01-14 2010-12-29 浙江大学 薄膜锂离子电池的负极材料及其制备方法
CN102916161B (zh) * 2011-10-21 2016-02-17 苏州大时代能源科技有限公司 一种锂离子电池的电极复合材料及其制备方法
CN102437313A (zh) * 2011-12-08 2012-05-02 中国电子科技集团公司第十八研究所 一种大功率金属锂电池用负电极
US9166220B2 (en) * 2012-02-13 2015-10-20 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same
WO2013140940A1 (fr) * 2012-03-22 2013-09-26 住友電気工業株式会社 Batterie secondaire au lithium
CN102683740B (zh) * 2012-05-21 2014-10-22 龙能科技（苏州）有限公司 锂离子电池
CN102694149B (zh) * 2012-06-07 2014-11-12 广东工业大学 一种动力型锂离子电池用电极的制造设备及其制造方法
CN103794800B (zh) * 2012-11-02 2016-12-21 华为技术有限公司 锂电池集流体、极片和锂电池及其制备方法、锂电池应用
CN104347882A (zh) * 2013-07-25 2015-02-11 谢振华 一种锂电池
CN103682257B (zh) * 2013-12-27 2016-11-16 安徽亿诺新能源有限责任公司 锂二次电池的正极电极制备工艺
CN105018776B (zh) * 2014-04-30 2017-09-29 中国科学院金属研究所 一种多孔铜箔的制备工艺及其应用
US10566582B2 (en) * 2016-06-23 2020-02-18 Intel Corporation Battery utilizing device cavity
CN106972174B (zh) * 2017-04-14 2019-06-28 华中科技大学 一种用于液态金属电池的双层负极集流体及其制备方法
CN109037591B (zh) * 2018-08-02 2020-12-25 桑德新能源技术开发有限公司 电极与全固态电池及其制备方法与锂离子电池
CN109390643A (zh) * 2018-10-11 2019-02-26 南京宁智高新材料研究院有限公司 一种用于电池在低温下冷启动的三维电极加热方法
CN113539690A (zh) * 2021-05-26 2021-10-22 中天超容科技有限公司 电池电容及其制备方法

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Publication number Priority date Publication date Assignee Title
US20180183040A1 (en) * 2015-09-02 2018-06-28 The Regents Of The University Of Michigan Electrochemical device including three-dimensional electrode substrate
EP3345236A4 (fr) * 2015-09-02 2019-01-23 The Regents Of The University Of Michigan Dispositif électrochimique incluant un substrat d'électrode en trois dimensions
CN114883575A (zh) * 2022-05-09 2022-08-09 清华大学 锂离子电池及其制备方法

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