Plasma activation and atomic layer deposition of TiO2 on polypropylene membranes for improved performances of lithium-ion batteries

Abstract Atomic layer deposition (ALD) of TiO2 was applied on porous polypropylene (PP) membranes which were used as separators in lithium-ion batteries (LIBs) composed of Li4Ti5O12 (LTO) anode/Li cathode. Without plasma activation on the bare PP membrane, the initial deposition of TiO2 was based on the subsurface nucleation mechanism, which prevented the formation of a conformal hydrophilic TiO2 layer at low ALD cycles. The improvement of wettability of the PP membrane to the electrolyte could only be achieved at high ALD cycles up to 500. However, the severe narrowing of membrane pores counterbalanced the wetting enhancement, which hardly improved the performance of the LIBs. Plasma pretreatment was efficient to generate active groups on the highly chemically inert surface of polypropylene membranes, thus ultrathin TiO2 films could be conformally deposited by ALD on the membrane surface based on the layer-by-layer mechanism at cycles as low as 20. Such a conformal ultrathin layer of TiO2 was confirmed to concurrently overcome both the thermal shrinkage and poor wettability of the PP membranes. Beneficial from the improved wettability at no expense of pore size, the electrochemical performances of LIBs such as specific discharge capacities at different discharge rates were upgraded.

[1]  Zhi‐Kang Xu,et al.  Covalent attachment of phospholipid analogous polymers to modify a polymeric membrane surface: a novel approach. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[2]  Lin Gu,et al.  Rutile-TiO2 nanocoating for a high-rate Li4Ti5O12 anode of a lithium-ion battery. , 2012, Journal of the American Chemical Society.

[3]  J. Falconer,et al.  Photocatalytic and thermal catalytic oxidation of acetaldehyde on Pt/TiO2 , 1998 .

[4]  Steven M. George,et al.  Improved Functionality of Lithium‐Ion Batteries Enabled by Atomic Layer Deposition on the Porous Microstructure of Polymer Separators and Coating Electrodes , 2012 .

[5]  Dong-Won Kim,et al.  Enhancement of thermal stability and cycling performance in lithium-ion cells through the use of ceramic-coated separators , 2010 .

[6]  P. Kritzer Nonwoven support material for improved separators in Li–polymer batteries , 2006 .

[7]  Yurij M. Volfkovich,et al.  Lithium Ion Batteries , 2015 .

[8]  Yong Wang,et al.  Hydrophilization of porous polypropylene membranes by atomic layer deposition of TiO2 for simultaneously improved permeability and selectivity , 2013 .

[9]  Y. Nho,et al.  High density polyethylene membrane filled with alumina prepared by a gamma ray irradiation. , 2011, Journal of nanoscience and nanotechnology.

[10]  Li-ping Zhu,et al.  Preparation of PVDF/PEO-PPO-PEO blend microporous membranes for lithium ion batteries via thermally induced phase separation process , 2008 .

[11]  C. Schroën,et al.  Membrane modification to avoid wettability changes due to protein adsorption in an emulsion/membrane bioreactor. , 1993 .

[12]  Yong Wang,et al.  PVDF membranes with simultaneously enhanced permeability and selectivity by breaking the tradeoff effect via atomic layer deposition of TiO2 , 2013 .

[13]  M. Ritala,et al.  Atomic Layer Deposition of Nanostructured TiO2 Photocatalysts via Template Approach , 2007 .

[14]  S. George Atomic layer deposition: an overview. , 2010, Chemical reviews.

[15]  S. George,et al.  Nucleation and Growth during Al2O3 Atomic Layer Deposition on Polymers , 2005 .

[16]  M. Yoshio,et al.  Lithium-ion batteries , 2009 .

[17]  Myung-Hyun Ryou,et al.  Mussel‐Inspired Polydopamine‐Treated Polyethylene Separators for High‐Power Li‐Ion Batteries , 2011, Advanced materials.

[18]  M Rosa Palacín,et al.  Recent advances in rechargeable battery materials: a chemist's perspective. , 2009, Chemical Society reviews.

[19]  Pankaj Arora,et al.  Battery separators. , 2004, Chemical reviews.

[20]  Mato Knez,et al.  Greatly Increased Toughness of Infiltrated Spider Silk , 2009, Science.

[21]  Shengbo Zhang A review on the separators of liquid electrolyte Li-ion batteries , 2007 .

[22]  P. Bruce,et al.  Nanomaterials for rechargeable lithium batteries. , 2008, Angewandte Chemie.

[23]  M. Rosa Palacín,et al.  New British Standards , 1979 .

[24]  Ken Tomabechi,et al.  Energy Resources in the Future , 1994 .

[25]  W. Jin,et al.  Atomic layer deposition of alumina on porous polytetrafluoroethylene membranes for enhanced hydrophilicity and separation performances , 2012 .

[26]  Li-ping Zhu,et al.  Enhanced performance of modified HDPE separators generated from surface enrichment of polyether chains for lithium ion secondary battery , 2013 .

[27]  J. Yamaki,et al.  A consideration of lithium cell safety , 1999 .

[28]  Takashi Nishimura,et al.  A powder particle size effect on ceramic powder based separator for lithium rechargeable battery , 2005 .

[29]  Kang Xu,et al.  An inorganic composite membrane as the separator of Li-ion batteries , 2005 .

[30]  Sung Won Choi,et al.  An Electrospun Poly(vinylidene fluoride) Nanofibrous Membrane and Its Battery Applications , 2003 .

[31]  M. Ritala,et al.  Surface modification of thermoplastics by atomic layer deposition of Al2O3 and TiO2 thin films , 2008 .

[32]  Tatsuo Nakamura,et al.  Silica-Composite Nonwoven Separators for Lithium-Ion Battery: Development and Characterization , 2008 .

[33]  K. Choo,et al.  Hydrophilic modification of polypropylene microfiltration membranes by ozone-induced graft polymerization , 2000 .

[34]  E. Giannelis,et al.  Nanoparticle-coated separators for lithium-ion batteries with advanced electrochemical performance. , 2011, Physical chemistry chemical physics : PCCP.

[35]  Lixia Yuan,et al.  Development and challenges of LiFePO4 cathode material for lithium-ion batteries , 2011 .

[36]  Yong Wang,et al.  Plasma activation of porous polytetrafluoroethylene membranes for superior hydrophilicity and separation performances via atomic layer deposition of TiO2 , 2013 .