WO2015116938A1 - Liants de polymère électroactifs pour anodes en silicium - Google Patents

Liants de polymère électroactifs pour anodes en silicium Download PDF

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Publication number
WO2015116938A1
WO2015116938A1 PCT/US2015/013787 US2015013787W WO2015116938A1 WO 2015116938 A1 WO2015116938 A1 WO 2015116938A1 US 2015013787 W US2015013787 W US 2015013787W WO 2015116938 A1 WO2015116938 A1 WO 2015116938A1
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WO
WIPO (PCT)
Prior art keywords
silicon
polymer binder
group
binder
anode
Prior art date
Application number
PCT/US2015/013787
Other languages
English (en)
Inventor
Donghai Wang
Jiangxuan SONG
Original Assignee
The Penn State Research Foundation
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 The Penn State Research Foundation filed Critical The Penn State Research Foundation
Publication of WO2015116938A1 publication Critical patent/WO2015116938A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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

  • Embodiments of the invention relate to anodes for use with lithium-ion batteries, and particularly to binders used in those anodes. Description of the Related Art
  • LIBs Lithium-ion batteries
  • HEV hybrid electric vehicles
  • EV electric vehicles
  • Si silicon
  • nanostructured silicon include preparation of Si nanoparticles, porous Si materials, and core-shell structured Si nanowires to prevent the agglomeration of Si. Although these silicon forms may relieve the strong inner stress upon the lithiation/delithiation process and improve the electrochemical performance of silicon anodes, electrode deformation and external cell expansion still occur due to the large volume change of Si. This limits the commercialization of Si materials.
  • the covalent chemical bonds between the carboxy groups of the binder and the partially hydrolyzed Si0 2 on the Si surface are believed to play an important role in the effective binding and improved cycling stability of Si anodes.
  • the use of such a large amount of binder results in a significant reduction in absolute anode capacity and energy density.
  • a high-modulus natural polysaccharide extracted from brown algae was reported to yield a reasonably stable Si anode compared with polymeric binders such as PVDF, PAA and CMC, but the reversible capacity is much smaller than the theoretical capacity of -3500 mAh/g.
  • a cross-linked binder comprising cyclic and linear polymers was utilized to enhance the electrochemical performance of Si anodes mitigating the large volume expansion of Si anodes upon lithiation. None of these approaches has shown sufficient promise for wide adoption.
  • Particular embodiments may provide an electro-active polymer binder for a
  • silicon anode comprising a poly(amic acid) comprising a plurality of hydride units and amine units.
  • the poly(amic acid) has the following formula:
  • n is between 1 and 100,000, between 2 and 100,000, and between 10 and 5000.
  • a further embodiment may provide silicon anode comprising the polymer binder reported above, with silicon and carbon.
  • the polymer binder, silicon, and carbon are present in amounts between 1-98%, 1-80%), and 1-80%) by weight, respectively.
  • Other embodiments provide a battery comprising the silicon anode reported above.
  • a silicon anode comprising silicon, carbon, and poly(amic acid).
  • a method for making a binder for a silicon anode comprising mixing an anhydride monomer selected from the group consisting of 5,5'- (perfluoropropane-2,2-diyl)bis(isobenzofuran-l ,3-dione), benzo[l ,2-c:4,5-c']difuran- 1,3,5,7-tetraone, and [5,5'-biisobenzofuran]-l,r,3,3'-tetraone with an amine monomer selected from the group consisting of 4,4'-oxydianiline, benzene- 1,4-diamine, and pyrimidine-2,4,6-triamine in a polar solvent; and step-polymerizing the anhydride monomer and the amine monomer to form a poly(amic acid) binder for a silicon anode.
  • anhydride monomer selected from the group consisting of
  • a further embodiment provides an electroactive polymer binder for a silicon
  • X and Y are selected
  • A is selected from the
  • silicon anode an electroactive polymer binder as reported above, with silicon and carbon.
  • silicon, and carbon may be present, for example, in amounts between 1-98%, 1-80%, and 1-80% by weight, respectively.
  • Embodiments also provide batteries using the anodes as reported above. BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 shows cycling stability of silicon anode with PDMA-ODA Poly(amic acid) binder.
  • the electrode is composed of Silicon, super P® carbon and PDMA-ODA polymer binder (6:2:2 weight ratio).
  • FIG. 2 shows coulombic efficiency of silicon anode with PDMA-ODA Poly(amic acid) binder.
  • the electrode is composed of Silicon, super P® carbon and polymer binder
  • FIG. 3 shows the voltage profiles of silicon anode with PDMA-ODA Poly(amic acid) binder.
  • the electrode is composed of Silicon, super P® carbon and polymer binder (6:2:2 weight ratio).
  • FIG. 4 shows cycling stability of silicon anode with PDMA-ODA Poly(amic acid) binder at high C-rate.
  • FIG. 5 shows the voltage profiles of silicon anode with PDMA-ODA Poly(amic acid) binder at 50°C.
  • the electrode is composed of Silicon, super P® carbon and polymer binder (50:35: 15 weight ratio).
  • FIG. 6 shows the voltage profiles of silicon anode with PDMA-ODA Poly(amic acid) binder at 50°C.
  • the electrode is composed of Silicon, super P® carbon and polymer binder (50:35:15 weight ratio).
  • FIG. 7 shows the coloumbic efficiency of silicon anode with PDMA-ODA
  • FIG. 8 shows the voltage profiles of silicon anode with PDMA-ODA Poly(amic acid) binder.
  • the electrode is composed of Silicon, super P® carbon and polymer binder
  • the Si loading is 2.75 mg/cm .
  • FIG. 9 shows the coulombic efficiency of silicon anode with PDMA-ODA
  • the electrode is composed of Silicon, super P and polymer binder (50:35: 15 weight ratio).
  • poly(amic acid) silicon anode binder typically, the poly(amic acid) exhibits numerous repeat units derived from hydride units and amine unites, as shown in the structure below.
  • the repeat units (n) can range from 1-100, 000.
  • Rl can be -COOH, -OH, -CONH 2 , -CHO, -NH 2 , and ;
  • X and Y are selected independently and are between 1-100,000.
  • the moieties represented by the A and B can be selected from any polymer-forming moieties known in the art.
  • Each polymer may include end caps, which may be, for example, one-COOH, -
  • a and B are independently selected and may be any polymer-forming moiety.
  • A is selected from the group consisting of CH 2 -CH 2 - ;
  • B is selected from the group consisting of
  • the poly(amic acid) binder is synthesized by using the anhydride and amine as precursors.
  • Some suitable precursors are shown in Table 1.
  • Preparation is by step-polymerization in a polar solvent.
  • the polar solvent may be, for example, Dimethylformamide (DMF), dimethylacetamide (DMAC), or N-Methyl- 2-pyrrolidone (NMP).
  • DMF Dimethylformamide
  • DMAC dimethylacetamide
  • NMP N-Methyl- 2-pyrrolidone
  • the poly(amic acid) with different repeat units can be obtained by selecting different anhydride and amine monomers. A typical step-polymerization is reported below.
  • the amine monomer is first dissolved in the polar solvent, followed by addition of an equimolar amount of anhydride monomer.
  • the solution is stirred at 0-5 °C for 5-10 hours to giving a viscous polymer binder solution.
  • the process is conducted under nitrogen or argon gas.
  • the polar solvent can be dimethylformamide (DMF), dimethylacetamide (DMAC), N-Methyl-2-pyrrolidone (NMP), or their mixture at an arbitrarily selected ratio.
  • DMF dimethylformamide
  • DMAC dimethylacetamide
  • NMP N-Methyl-2-pyrrolidone
  • Embodiments of the invention also provide silicon anodes that incorporate the binder.
  • These anodes typically include active material, carbon, and a polymer binder as reported above.
  • the amounts of each substance may vary, in a typical embodiment the ingredients are present in the following weight ranges:
  • Active material from 1-34 wt%; Carbon from 1 -34 wt %; Binder from 1- 34 wt%.IV. Examples
  • pyromellitic dianhydride (PMDA, 99%, Acros), oxydianiline,(ODA, 99%, TCI), and 4,4-hexafluoroisopropylidenediphthalic anhydride (6FDA, 99%, are dried under vacuum for 5 hours at 50°C.
  • NMP N-Methyl-2-pyrrolidone
  • DMAc N,N- dimethylacetamide
  • each Anhydride may be used with each Amine; each Anhydride is not limited to use only with the amine in the same row in Table I .
  • Table 1 Chemical structure of alternative anhydride and amine for synthesis of poly(amic acid).
  • the composite cathodes are prepared by coating slurries containing active
  • the electrode is dried at 60 °C for 20 min, 100 °C for 2 hours, 150 °C for 2 hours min, 200 °C for 5 hours and finally at 250 °C for another 2 hours. Note that the above drying process is performed under high vacuum.
  • Electrochemical tests are performed by using 2016 coin-type half cells assembled with lithium metal as the counter in an argon filled glove box.
  • the composite cathodes are prepared by coating slurries containing active materials (60wt.%), Super P acetylene black (20wt.%), and poly(amic acid binder ( 20wt.%) on copper foil.
  • the typical loading of the electrode is 1 mg/cm 2 .
  • the electrolyte consists of 1 mol/L LiPF 6 in a mixture of ethylene carbonate, diethyl carbonate and dimethyl carbonate (EC: DEC: DMC, 1 : 1 : 1 by volume) and fluoroethylene carbonate (FEC, 10vol.%).
  • the FEC additive can increase the cycling efficiency of silicon anodes, due to the formation of a more stable SEI layer.
  • a galvanostatic cycling test is carried out at different constant current densities between 0.01 and 1.5V vs Li/Li + on a BT2000 battery testing system (Arbin Instruments, USA). The specific capacity is calculated on the basis of the weight of the active materials.

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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)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une série de liants de poly(amide-acide) basés sur différents monomères de dianhydride et amine. Ces polymères fonctionnels ont une bonne compatibilité avec une particule de silicium dans un solvant organique polaire et peuvent, in-situ, former une intercouche SEI artificielle stable pendant les plusieurs cycles initiaux. De plus, ces liants ont également des performances mécaniques adaptées pour adapter les changements de volume importants de l'anode de silicium pendant le cyclage. Ceux-ci peuvent significativement améliorer les performances électrochimiques d'une anode de silicium, en particulier à haute température et à une charge élevée de matériaux actifs.
PCT/US2015/013787 2014-01-31 2015-01-30 Liants de polymère électroactifs pour anodes en silicium WO2015116938A1 (fr)

Applications Claiming Priority (2)

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US201461934171P 2014-01-31 2014-01-31
US61/934,171 2014-01-31

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106129347A (zh) * 2016-06-24 2016-11-16 深圳大学 多孔硅复合负极材料及其制备方法和锂离子电池
US20230089292A1 (en) * 2021-09-13 2023-03-23 StoreDot Ltd. Self healing lithium-ion battery
CN115863651A (zh) * 2022-12-29 2023-03-28 蜂巢能源科技股份有限公司 一种原位包覆高压电正极材料和制备方法及其用途

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070048609A1 (en) * 2005-08-29 2007-03-01 Tomohiro Ueda Negative electrode for non-aqueous electrolyte secondary battery, producing method therefor, and non-aqueous electrolyte secondary battery
US20080124631A1 (en) * 2006-06-30 2008-05-29 Sanyo Electric Co., Ltd. Lithium secondary battery and method of manufacturing the same
US20110305951A1 (en) * 2009-03-31 2011-12-15 Ube Industries, Ltd. Binder resin precursor solution composition for electrode
US20120168688A1 (en) * 2009-09-30 2012-07-05 Ube Industries, Ltd. Binder resin composition for electrode, electrode mixture paste, and electrode
US20130260223A1 (en) * 2012-04-03 2013-10-03 Hyesun Jeong Water soluble binder composition, method of producing the same and electrode for rechargeable battery employing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070048609A1 (en) * 2005-08-29 2007-03-01 Tomohiro Ueda Negative electrode for non-aqueous electrolyte secondary battery, producing method therefor, and non-aqueous electrolyte secondary battery
US20080124631A1 (en) * 2006-06-30 2008-05-29 Sanyo Electric Co., Ltd. Lithium secondary battery and method of manufacturing the same
US20110305951A1 (en) * 2009-03-31 2011-12-15 Ube Industries, Ltd. Binder resin precursor solution composition for electrode
US20120168688A1 (en) * 2009-09-30 2012-07-05 Ube Industries, Ltd. Binder resin composition for electrode, electrode mixture paste, and electrode
US20130260223A1 (en) * 2012-04-03 2013-10-03 Hyesun Jeong Water soluble binder composition, method of producing the same and electrode for rechargeable battery employing

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106129347A (zh) * 2016-06-24 2016-11-16 深圳大学 多孔硅复合负极材料及其制备方法和锂离子电池
US20230089292A1 (en) * 2021-09-13 2023-03-23 StoreDot Ltd. Self healing lithium-ion battery
CN115863651A (zh) * 2022-12-29 2023-03-28 蜂巢能源科技股份有限公司 一种原位包覆高压电正极材料和制备方法及其用途

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