WO2019106594A1 - Anode sba-15/c pour une batterie lithium-ion et son procédé de fabrication - Google Patents

Anode sba-15/c pour une batterie lithium-ion et son procédé de fabrication Download PDF

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Publication number
WO2019106594A1
WO2019106594A1 PCT/IB2018/059455 IB2018059455W WO2019106594A1 WO 2019106594 A1 WO2019106594 A1 WO 2019106594A1 IB 2018059455 W IB2018059455 W IB 2018059455W WO 2019106594 A1 WO2019106594 A1 WO 2019106594A1
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anode
lithium
ion battery
sba
composite material
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PCT/IB2018/059455
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English (en)
Inventor
Germán LENER
Ezequiel Leiva
Daniel Barraco Diaz
Manuel OTERO
Original Assignee
Ypf Tecnologia S.A.
SORIA, Juan C.
Consejo Nacional De Investigaciones Cientificas Y Tecnicas (Conicet)
Universidad Nacional De Cordoba
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Priority claimed from US15/827,276 external-priority patent/US10608246B2/en
Priority claimed from ARP170103340A external-priority patent/AR110279A1/es
Application filed by Ypf Tecnologia S.A., SORIA, Juan C., Consejo Nacional De Investigaciones Cientificas Y Tecnicas (Conicet), Universidad Nacional De Cordoba filed Critical Ypf Tecnologia S.A.
Priority to EP18829476.3A priority Critical patent/EP3718158A1/fr
Publication of WO2019106594A1 publication Critical patent/WO2019106594A1/fr

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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • 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
    • H01M4/13—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of 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
    • 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

  • the present invention relates to the technical area of electrochemical devices for obtaining and storing electrical energy.
  • the present invention relates to an SBA-15/C anode for a lithium-ion battery and to a method of manufacturing said anode.
  • Lithium-ion batteries are widely used in electronic devices, electric vehicles, and for the storage of renewable energies such as photovoltaic and wind energies, among others. LIBs allow the storage of this energy for later use, being it possible to adapt them to different energy demand conditions.
  • Patent application US 2017/260057 describes a process for the manufacture of nanoparticles of formula SiOx, where x is comprised between 0.8 and 1.2, by means of a fusion reaction between S1O2 and Si, at a temperature of at least 1410°C.
  • the charge/discharge capacity should be improved by an adequate ionic conductivity during the electrochemical process of Li + ion migration.
  • the ionic and electrical conductivities of the electrode materials must be improved. In this way, the high specific capacity could be maintained, even at high current densities.
  • Patent applications CN 106159222 and CN104701496 describe anodes for a LIB comprising a carbonaceous structure of high electrical conductivity, as well as Co and Sn nanoparticles. Although these anodes are manufactured from a material based on S1O2, said material is subsequently removed from the anodes.
  • Application CN 104528740 is directed to a composite material comprising S1O2 and carbon, with a carbon content of less than 20%. None of these documents teaches or suggests the anodes and manufacturing methods of the present invention.
  • Si02-based materials are attractive alternatives for the manufacture of Si- based anodes, since silica is one of the most abundant elements in Earth's crust and since S1O2 clays with complex porous nanostructures are well known.
  • the synthesis of nanoporous materials from S1O2 is generally simple and inexpensive.
  • these compounds could be used as a model material for complex natural clays, which could be used to store energy at a reduced cost.
  • the main drawback of silica is the insulation characteristics thereof. Electron conduction is not possible with pure S1O2, thus limiting possible reduction to Si and other silicon products.
  • the present invention aims to solve the drawbacks of the prior art, by providing an anode for a LIB based on a composite material made from highly ordered S1O2, and including a conductive carbon structure, so as to improve ionic and electrical conductivities, thus avoiding long, complex and costly syntheses employed in similar inventions of the prior art.
  • various mesoporous materials made from S1O2 can be used.
  • conductivities are improved, since a conductive skeleton is generated that improves the conversion of S1O2 to Si and other products.
  • Said other products are, in turn, advantageous during the operation of a LI B, since they mitigate the effect of the volumetric expansion during the lithiation process and improve the ionic diffusion of Li + .
  • a composite material for lithium-ion battery anodes comprising a composite material comprising carbon nanofibers and S1O2.
  • the composite material has a high carbon content, resulting in improved electrical conduction properties.
  • an anode for a lithium-ion battery comprising a composite material comprising carbon nanofibers and S1O2.
  • the composite material has a high carbon content, resulting in improved electrical conduction properties thereof.
  • a lithium-ion battery comprising an anode that comprises a composite material comprising carbon nanofibers and S1O2.
  • said composite material has a porous structure comprising mesopores interconnected by micropores, wherein said carbon nanofibers occupy the pore space of said porous structure.
  • the carbon content in said composite material is about 45% by weight.
  • said mesopores have a mean diameter of about 5 nm and said micropores have a mean diameter of about 1 nm.
  • said carbon source is sucrose.
  • said acid is sulfuric acid.
  • the drying stage c) is carried out at 900°C under an argon atmosphere.
  • Figure 1 shows the nitrogen adsorption/desorption isotherms of synthesized materials and the hysteresis curves corresponding to the different porous structures of the materials obtained according to an exemplary embodiment of the present invention.
  • Figure 2 shows the results of thermogravimetric analysis in air of a composite material according to an exemplary embodiment of the present invention.
  • Figures 3a-3f show SEM micrographs of the materials obtained in an exemplary embodiment of the present invention.
  • Figures 4a-4c show experimental results of electrochemical measurements performed on the composite material obtained in an exemplary embodiment of the present invention.
  • Figures 5a-5b show the experimental results of electrochemical measurements performed on the composite material obtained in a first comparative experiment.
  • Figures 6a-6b show the experimental results of electrochemical measurements performed on the composite material obtained in a second comparative experiment.
  • the anode for a lithium-ion battery of the present invention can be obtained from a starting porous material comprising S1O2, treated with a carbon source in order to obtain a composite material.
  • the starting porous material is a material made from S1O2 known as SBA-15.
  • Said compound has a porous structure of mesopores interconnected by micropores.
  • the composite material thus formed is designated as SBA-15/C.
  • the advantage of using this composite material as an anode in lithium-ion batteries lies in a surprising synergistic effect between S1O2 and the carbonaceous structure.
  • Li storage can be produced according to the following partial reaction:
  • the composite material SBA-15/C has a specific capacity of 450 mAhg ⁇ 1 , superior to that of graphite commercially used in similar applications. Surprisingly, it is observed that it is possible to discharge the anode manufactured from the composite material at high current rates, without meaningfully changing its specific capacity.
  • the SBA-15 material was synthesized according to the method reported by Zhao et al. (see e.g. Cano, L. A..; Garcia Blanco, A. A.; Lener, G.; Marchetti, S. G.; Sapag, K. Catal. Today 2016, Zhao, D.; Huo, Q.; Feng, J.; Chmelka, B. F.; Stucky, G. D. J. Am. Chem. Soc. 1998, 120, 6024-6036; Zhao, D. Science (80-J (1998), 279, 548-552)
  • Pluronic triblock copolymer P123 (E020-P070-E020) was used as a structuring organic compound. 12 g of P123 were dissolved in 360 ml of ultra-pure water and 60 ml of 37% w/w HCI solution. The mixture was stirred for 3 h at 40°C until a clear solution was obtained. To this solution, 27 ml of tetraethylorthosilicate (TEOS) was added dropwise as a silica source. Once the TEOS was added, the mixture was allowed at 40°C under stirring for 24 h. The mixture was then allowed to age 24 h without stirring at 40°C. The solid was filtered and washed at room temperature with ultra-pure water. Then, the solid was dried at 80°C and calcined at 500°C for 6 h, using a heating ramp rate of 1 0 C/min starting from room temperature.
  • TEOS tetraethylorthosilicate
  • the synthesis of the composite material SBA-15/C was carried out by impregnation with a sucrose solution in sulfuric acid medium. A ratio of 2:1 sucrose/SBA-15 and 5 ml of ultra-pure water per gram of sucrose was used. The mixture SBA- 15/sucrose was stirred for 2 h, then 0.14 ml of H2SO4 (98% w/w) was added per ml of water and it was left under stirring for 1 h. The mixture was dried in air at 80°C for 6 h. Subsequently, a thermal treatment was carried out in a N2 inert atmosphere from room temperature up to 700°C for 5 h with a heating ramp rate of 2°C/min.
  • the resulting sample was divided into two parts. One part was subjected to another thermal treatment at 900°C in a N2 inert atmosphere to obtain the composite material SBA-15/C. The other part was treated with NaOH at 60°C for 5 h in order to dissolve the S1O2 matrix.
  • This carbonaceous structure was subjected to thermal treatment in N2 at 900°C for 5 h to obtain a material known as CMK-3 (see Shin, HJ, Ryoo, R.; Kruk, M.; Jaroniec, M. Chem. Commun. 1 , (2001), 349-350.
  • the final temperature control is of utmost importance in order to desorb functional groups and obtain a material with optimal electrical conduction.
  • Electrochemical measurements [046] The study of the electrochemical performance of the anodes was carried out with a Swagelok type T cell, using a metallic lithium disk of 8 mm in diameter as counter-electrode.
  • the working electrode was prepared with the tested material, PVDF as binder and super P carbon as conductive material, in a 80:10:10 ratio.
  • the mixture of the tested material was deposited on a copper foil as a current collector and dried at 80°C for 12 h.
  • Figure 1 shows the isotherms of nitrogen adsorption/desorption at 77 K of the synthesized materials. There, the hysteresis curves corresponding to the mesoporous structure can be observed. The slope at low relative pressures correspond to the microporous structure, characteristic of SBA-15 and CMK-3 materials.
  • the mean diameter of mesopores was 8 nm and 5 nm for SBA-15 and CMK- 3 respectively, while the mean diameter of micropores was approximately 1 nm for both materials.
  • CMK-3 is obtained by filling pores of SBA-15 with a carbonaceous structure. Therefore, CMK-3 represents the inverse replica of SBA- 15. Therefore, having successfully obtained CMK-3 indicates that SBA-15/C material has pores filled with carbonaceous material.
  • Figure 2 shows the thermogravimetric analysis of SBA-15/C in air. A mass loss of 45% at 600°C is observed due to decomposition of C to CO2. Therefore, the S1O2/C ratio in the material was 55/45. Therefore, the C content is significantly higher than that of the composite materials described in the prior art.
  • Figures 3a-3f show SEM micrographs of SBA-15/C and CMK-3 in different magnifications. With respect to SBA-15, uniform particles of around 300 nm are observed (Figs. 3a and 3b) and the interlaminar S1O2/C structure can also be observed at nanometric scale (Fig. 3c). [052] On the other hand, SEM micrographs of CMK-3 show a particle size of 200 nm (Figs. 3d and 3e) and the characteristic nanometric interlaminate that generates the porous structure of the material (Fig. 3f).
  • composite material SBA-15/C is a three-dimensional array of S1O2 nanotubes of 8 nm in diameter interconnected by nanotubes of ca. 1 nm in diameter.
  • the nanotubes are filled with carbon treated at 900°C in inert gas to obtain a conductive material so that the electrons can diffuse through the material to contact S1O2 and reduce it to generate Si in-operation.
  • the metallic Si is semiconductor, so that the carbon coating allows maximizing the conductivity in charging/discharging processes.
  • Figure 4a shows the specific capacity obtained from galvanostatic charge/discharge profiles of SBA-15/C as a function of the number of charge/discharge cycles performed. An irreversible initial charge capacity of 1300 mAhg- 1 can be observed. From cycle number 2 and up to cycle number 300, a 450 mAhg ⁇ 1 stable charge/discharge capacity is observed, with an average coulombic efficiency of 93%, calculated between cycles 3 and 300.
  • Figure 4b shows the derivative of charge with respect to potential as a function of the potential. From this derivative, the processes that occur during charging/discharging can be observed.
  • charge cycle number 1 a cathodic peak around 0.75 V is observed, corresponding to the formation of the solid/electrolyte interface (SEI) and also a wide peak near 0.1 V that can be attributed to the reduction from S1O2 to metallic Si and lithium silicate and lithium oxide, as indicated in partial reactions (1) to (4) above.
  • SEI solid/electrolyte interface
  • the charging current was adjusted for the electrode to charge in 20 hours (C/20) and the discharge current was adjusted so that the electrode was discharged in 20 hours (C/20).
  • the specific discharge capacity was 498 mAhg- 1 .
  • the composite material has a mass ratio S1O2/C of 55/45. Considering S1O2 as an active species and excluding from consideration the carbonaceous material, it can be concluded that the theoretical capacity of the material containing Si should be 905.5 mAhg ⁇ 1 . If, on the other hand, a capacity of 250 mAhg ⁇ 1 is attributed to the carbonaceous material (see results for CMK3 below), a theoretical capacity of 701 mAhg ⁇ 1 is obtained for the material comprising silica.
  • Figure 5b shows the derivative of charge with respect to potential for the same material. Peaks associated with irreversible processes are observed in the first charge cycle, probably due to the formation of SEI and other irreversible reductions, and then a pseudo-capacitive behavior is observed. b) CMK-3
  • CMK- 3 The carbonaceous matrix of the composite material SBA-15/C is called CMK- 3. As described above, this material has a porous structure of mesoporous nanotubes 5 nm in diameter, joined by microporous nanotubes of 1 nm in diameter.
  • Figure 6a shows the specific capacity obtained from the galvanostatic charge/discharge profiles of CMK-3. An initial charge capacity of 3000 mAhg ⁇ 1 (not shown in the graph due to scale issues) and an initial discharge capacity of 446 mAhg ⁇ 1 showing an irreversible capacity of 2554 mAhg-1 were found. The charging and discharging values are stabilized after cycle number 50 and remain constant up to cycle number 100 in values of 250 mAhg ⁇ 1 .
  • Figure 6b shows the derivative of charge with respect to potential for the CMK3 material. Peaks of cathodic current at 0.68 and 0.9 V are found in cycle number one. These correspond to irreversible processes associated with the formation of the solid/electrolyte interface in the mesopores and in the micropores.
  • this material has an apparent specific surface area of 1050 m 2 /g, so the filling of pores with electrolyte results in a significant current consumption due to electrolyte decomposition and reduction of superficial functional groups which is evidenced in the high Initial specific capacity.
  • Subsequent cycles in the dQ/dE plot in Figure 6b do not show any specific lithium ion storage process, but rather an apparent pseudo-capacitive behavior of the material with good ion storage capacity, probably due to the charging of the double layer.
  • the method of the present invention is an economically favorable alternative, since it does not involve any of the mentioned extreme conditions.

Abstract

La présente invention concerne une anode pour une batterie lithium-ion et son procédé de fabrication. L'anode est fabriquée à partir d'un matériau composé de Si et C connu sous le nom de SBA-15/C ayant une structure poreuse de mésopores interconnectés par des micropores, des nanofibres de carbone occupant l'espace poreux de la structure poreuse. L'anode présente des propriétés de conductivité améliorées et permet d'atténuer les inconvénients liés à la dilatation volumétrique de l'anode pendant le fonctionnement d'une batterie lithium-ion.
PCT/IB2018/059455 2017-11-30 2018-11-29 Anode sba-15/c pour une batterie lithium-ion et son procédé de fabrication WO2019106594A1 (fr)

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US15/827,276 2017-11-30
US15/827,276 US10608246B2 (en) 2017-11-30 2017-11-30 SBA-15/C anode for a lithium-ion battery and manufacturing method thereof
AR20170103340 2017-11-30
ARP170103340A AR110279A1 (es) 2017-11-30 2017-11-30 Ánodo de sba-15/c para una batería de ión-litio y método de fabricación del mismo

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