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Highly reliable quinone-based cathodes and cellulose nanofiber separators: toward eco-friendly organic lithium batteries

Abstract

Recently, organic compounds are considered as promising candidates for application in next-generation energy storage systems to overcome the disadvantages of conventional inorganic cathode materials, including their low specific capacity and poor disposal systems. In particular, pillar[5]quinone (P5Q) is very effective as it provides active sites that favor Li uptake and promote a high theoretical capacity. Herein, we propose P5Q-derived cathodes, which are enveloped in multi-walled carbon nanotubes and cellulose nanofibers (CNFs), fabricated by a simple vacuum-filtering method. The designed cathode solves the issues associated with organic materials, including their high solubilities in aprotic electrolytes and low conductivities. Furthermore, CNFs are introduced as alternatives to conventional polyolefin separators. CNF separators can effectively suppress the dissolution of active materials in liquid electrolytes. In addition, CNFs improve ionic conductivity (0.88 mS cm−1), electrolyte wettability (electrolyte uptake: 333.41%, porosity: 70 ± 5%), and thermal shrinkage in contrast to conventional polyolefin separators. The Li-ion battery, assembled with the suggested P5Q cathode and CNF separator, exhibits highly stable capacity retention (76.5% after 50 cycles at a 0.2 C rate) and good rate capability, although an organic electrolyte is used.

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References

  • Ahmad A et al (2017) A hierarchically porous hypercrosslinked and novel quinone based stable organic polymer electrode for lithium-ion batteries. Electrochim Acta 255:145–152

    CAS  Google Scholar 

  • Ahn Y et al (2015) Enhanced electrochemical capabilities of lithium ion batteries by structurally ideal AAO separator. J Mater Chem A 3:10715–10719

    CAS  Google Scholar 

  • Armand M et al (2008) Building better batteries. Nature 451:652–657

    CAS  PubMed  Google Scholar 

  • Belanger RL et al (2019) Difusion control of organic cathode materials in lithium metal battery. Sci Rep 9:1213

    PubMed  PubMed Central  Google Scholar 

  • Chen H et al (2008) From biomass to a renewable LiXC6O6 organic electrode for sustainable li-ion batteries. Chemsuschem 1:348–355

    CAS  PubMed  Google Scholar 

  • Chen W et al (2018) Nanocellulose: a promising nanomaterial for advanced electrochemical energy storage. Chem Soc Rev 47:2837–2972

    CAS  PubMed  Google Scholar 

  • Chen D et al (2019) An upgraded lithium ion battery based on a polymeric separator incorporated with anode active materials. Adv Energy Mater 9:1803627

    Google Scholar 

  • Chun SJ et al (2012) Eco-friendly cellulose nanofiber paper-derived separator membranes featuring tunable nanoporous network channels for lithium-ion batteries. J Mater Chem 22:16618–16626

    CAS  Google Scholar 

  • Du X et al (2017) Nanocellulose-based conductive materials and their emerging applications in energy devices—a review. Nano Energy 35:299–320

    CAS  Google Scholar 

  • Dunn B et al (2011) Electrical energy storage for the grid: a battery of choices. Science 334:928–935

    CAS  PubMed  Google Scholar 

  • Ellis BL et al (2010) Positive electrode materials for Li-ion and Li-batteries. Chem Mater 22:691–714

    CAS  Google Scholar 

  • Hanyu Y et al (2012) Rechargeable quasi-solid state lithium battery with organic crystalline cathode. Sci Rep 2:453

    PubMed  PubMed Central  Google Scholar 

  • Hanyu Y et al (2014) Multielectron redox compounds for organic cathode quasi-solid state lithium battery. J Electrochem Soc 161:A6–A9

    CAS  Google Scholar 

  • He X et al (2016) Wafer-scale monodomain films of spontaneously aligned single-walled carbon nanotubes. Nat Nanotechnol 11:633–638

    CAS  PubMed  Google Scholar 

  • Huan L et al (2017) Computational electrochemistry of pillar[5]quinone cathode material for lithium-ion batteries. Comput Mater Sci 137:233–242

    CAS  Google Scholar 

  • Huang W et al (2013) Quasi-solid-state rechargeable lithium-ion batteries with a calix[4]quinone cathode and gel polymer electrolyte. Angew Chem Int Ed 52:9162–9166

    CAS  Google Scholar 

  • Huang P et al (2016) A versatile method for producing functionalized cellulose nanofibers and their application. Nanoscale 8:3753–3759

    CAS  PubMed  Google Scholar 

  • Ishiara K (2002) 5th ecobalance conference. Tsukuba

  • Kang K et al (2006) Electrodes with high power and high capacity for rechargeable lithium batteries. Science 311:977–980

    CAS  PubMed  Google Scholar 

  • Khurana R et al (2014) Suppression of lithium dendrite growth using cross-linked polyethylene/poly(ethylene oxide) electrolytes: a new approach for practical lithium-metal polymer batteries. Chem Soc 136:7395–7402

    CAS  Google Scholar 

  • Kim H et al (2018) Highly stable lithium metal battery with an applied three-dimensional mesh structure interlayer. J Mater Chem A 6:15540–15545

    CAS  Google Scholar 

  • Kim JH et al (2019) Nanomat Li–S batteries based on all-fibrous cathode/separator assemblies and reinforced Li metal anodes: towards ultrahigh energy density and flexibility. Energy Environ Sci 12:177–186

    CAS  Google Scholar 

  • Knoche T et al (2016) Effect of annealing temperature on pore formation in preparation of advanced polyethylene battery separator membranes. Mater Today Commun 8:23–30

    CAS  Google Scholar 

  • Kong BS et al (2009) Layer-by-layer assembly of graphene and gold nanoparticles by vacuum filtration and spontaneous reduction of gold ions. Chem Commun 16:2174–2176

    Google Scholar 

  • Larcher D et al (2015) Towards greener and more sustainable batteries for electrical energy storage. Nat Chem 7:19–29

    CAS  PubMed  Google Scholar 

  • Lee H et al (2016a) Structural modulation of lithium metal-electrolyte interface with three-dimensional metallic interlayer for high-performance lithium metal batteries. Sci Rep 6:30830

    CAS  PubMed  PubMed Central  Google Scholar 

  • Lee JH et al (2016b) High-energy-density lithium-ion battery using a carbon-nanotube-Si composite anode and a compositionally graded Li[Ni0.85Co0.05Mn0.10]O2 cathode. Energy Environ Sci 9:2152–2158

    CAS  Google Scholar 

  • Lee S et al (2019) The role of substituents in determining the redox potential of organic electrode materials in Li and Na rechargeable batteries: electronic effects vs. substituent-Li/Na ionic interaction. J Mater Chem A 7:11438

    CAS  Google Scholar 

  • Levi MD et al (2006) Unusually high stability of a poly(alkylquaterthiophene-alt-oxadiazole) conjugated copolymer in its n and p-doped states. Chem Commun 31:3299–3301

    Google Scholar 

  • Li L et al (2014) Advances and challenges for flexible energy storage and conversion devices and systems. Energy Environ Sci 7:2101–2122

    CAS  Google Scholar 

  • Liang Y et al (2012) Organic electrode materials for rechargeable lithium batteries. Adv Energy Mater 2:742–769

    CAS  Google Scholar 

  • Lin D et al (2017) Reviving the lithium metal anode for high-energy batteries. Nat Nanotechnol 12:194–206

    CAS  PubMed  Google Scholar 

  • Liu K et al (2011) Poly(2,5-dihydroxy-1,4-benzoquinonyl sulfide) (PDBS) as a cathode material for lithium ion batteries. J Mater Chem 21:4125–4131

    CAS  Google Scholar 

  • Ma CW et al (2015) A paper-like micro-supercapacitor with patterned buckypaper electrodes using a novel vacuum filtration technique. In: 28th IEEE international conference on micro electro mechanical systems (MEMS), pp 1067–1070

  • Mauger A et al (2018) A comprehensive review of lithium salts and beyond for rechargeable batteries: progress and perspectives. Mater Sci Eng, R 134:1–21

    Google Scholar 

  • Mauger A et al (2019) Recent progress on organic electrodes materials for rechargeable batteries and supercapacitors. Materials 12:1770

    CAS  PubMed Central  Google Scholar 

  • Paakko M et al (2008) Long and entangled native cellulose I nanofibers allow flexible aerogels and hierarchically porous templates for functionalities. Soft Matter 4:2492–2499

    CAS  Google Scholar 

  • Pan R et al (2019) Sandwich-structured nano/micro fiber-based separators for lithium metal batteries. Nano Energy 55:316–326

    CAS  Google Scholar 

  • Pretsch E et al (2009) Structure determination of organic compounds tables of spectral data. Springer, Berlin

    Google Scholar 

  • Schon TB et al (2016) The rise of organic electrode materials for energy storage. Chem Soc Rev 45:6345–6404

    CAS  PubMed  Google Scholar 

  • Scrosati B et al (2010) Lithium batteries: status, prospects and future. J Power Sources 195:2419–2430

    CAS  Google Scholar 

  • Song Z et al (2009) Anthraquinone based polymer as high performance cathode material for rechargeable lithium batteries. Chem Commun 45:448–450

    Google Scholar 

  • Song Z et al (2013) Towards sustainable and versatile energy storage devices: an overview of organic electrode materials. Energy Environ Sci 6:2280–2301

    CAS  Google Scholar 

  • Takamura T et al (2004) A vacuum deposited Si film having a Li extraction capacity over 2000 mAh/g with a long cycle life. J Power Sources 129:96–100

    CAS  Google Scholar 

  • Tobjörk D et al (2011) Paper electronics. Adv Mater 23:1935–1961

    PubMed  Google Scholar 

  • Walker W et al (2010) Ethoxycarbonyl-based organic electrode for Li-batteries. J Am Chem Soc 132:6517–186523

    CAS  PubMed  Google Scholar 

  • Wang X et al (2013) An aqueous rechargeable lithium battery using coated Li metal as anode. Sci Rep 3:1401

    PubMed  PubMed Central  Google Scholar 

  • Wu HP et al (2013) An organic cathode material based on a polyimide/CNT nanocomposite for lithium ion batteries. J Mater Chem A 1:6366–6372

    CAS  Google Scholar 

  • Wu Y et al (2017) Quinone electrode materials for rechargeable lithium/sodium ion batteries. Adv Energy Mater 7:1700278–1700304

    Google Scholar 

  • Yan J et al (2012) Advanced asymmetric supercapacitors based on ni(oh)2/graphene and porous graphene electrodes with high energy density. Adv Funct Mater 22(632):2641

    Google Scholar 

  • Yao M et al (2012) Redox active poly(N-vinylcarbazole) for use in rechargeable lithium batteries. J Power Sources 202:364–368

    CAS  Google Scholar 

  • Yin Z et al (2018) Copper nanowire/multi-walled carbon nanotube composites as all-nanowire flexible electrode for fast-charging/discharging lithium-ion battery. Nano Res 11:769–779

    CAS  Google Scholar 

  • Zhan L et al (2008) PEDOT: cathode active material with high specific capacity in novel electrolyte system. Electrochim Acta 53:8319–8323

    CAS  Google Scholar 

  • Zhang SS et al (2007) A review on the separators of liquid electrolyte Li-ion batteries. J Power Sources 164:351–364

    CAS  Google Scholar 

  • Zhang H et al (2015) Preparation and characterization of a lithium-ion battery separator from cellulose nanofibers. Heliyon 1:e00032

    PubMed  PubMed Central  Google Scholar 

  • Zhu Z et al (2014) All-solid-state lithium organic battery with composite polymer electrolyte and pillar[5]quinone cathode. J Am Chem Soc 136:16461–16464

    CAS  PubMed  Google Scholar 

Download references

Acknowledgments

This research was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT, Ministry of Science and ICT) - Nano-Material Technology Development Program (2016M3A7B4910458) and Basic Science Research Program (2019R1A2C1009239).

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Writing—original draft preparation: [Gayeong Yoo], [Seonmi Pyo]; Formal analysis and investigation: [Gayeong Yoo], [Seonmi Pyo]; Methodology: [Gayeong Yoo], [Seonmi Pyo], [Youn Sang Kim]; Data curation and visualization: [Youn Jun Gong], [Jinil Cho], [Heebae Kim]; Conceptualization: [Youn Sang Kim], [Jeeyoung Yoo]; Writing- review and editing: [Jeeyoung Yoo]; Funding acquisition: [Youn Sang Kim], [Jeeyoung Yoo]; Supervision: [Youn Sang Kim], [Jeeyoung Yoo].

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Correspondence to Youn Sang Kim or Jeeyoung Yoo.

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Yoo, G., Pyo, S., Gong, Y.J. et al. Highly reliable quinone-based cathodes and cellulose nanofiber separators: toward eco-friendly organic lithium batteries. Cellulose 27, 6707–6717 (2020). https://doi.org/10.1007/s10570-020-03266-8

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  • DOI: https://doi.org/10.1007/s10570-020-03266-8

Keywords

  • Organic lithium batteries
  • Cellulose nanofibers
  • Carbon frame
  • Eco-friendly LIBs
  • Next generation batteries