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Yi Cui

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DOI: 10.1038/nnano.2007.411
2007
Cited 5,990 times
High-performance lithium battery anodes using silicon nanowires
DOI: 10.1126/science.1062711
2001
Cited 5,517 times
Nanowire Nanosensors for Highly Sensitive and Selective Detection of Biological and Chemical Species
Boron-doped silicon nanowires (SiNWs) were used to create highly sensitive, real-time electrically based sensors for biological and chemical species. Amine- and oxide-functionalized SiNWs exhibit pH-dependent conductance that was linear over a large dynamic range and could be understood in terms of the change in surface charge during protonation and deprotonation. Biotin-modified SiNWs were used to detect streptavidin down to at least a picomolar concentration range. In addition, antigen-functionalized SiNWs show reversible antibody binding and concentration-dependent detection in real time. Lastly, detection of the reversible binding of the metabolic indicator Ca2+ was demonstrated. The small size and capability of these semiconductor nanowires for sensitive, label-free, real-time detection of a wide range of chemical and biological species could be exploited in array-based screening and in vivo diagnostics.
DOI: 10.1038/35051047
2001
Cited 3,243 times
Indium phosphide nanowires as building blocks for nanoscale electronic and optoelectronic devices
DOI: 10.1126/science.291.5505.851
2001
Cited 3,122 times
Functional Nanoscale Electronic Devices Assembled Using Silicon Nanowire Building Blocks
Because semiconductor nanowires can transport electrons and holes, they could function as building blocks for nanoscale electronics assembled without the need for complex and costly fabrication facilities. Boron- and phosphorous-doped silicon nanowires were used as building blocks to assemble three types of semiconductor nanodevices. Passive diode structures consisting of crossed p- and n-type nanowires exhibit rectifying transport similar to planar p-n junctions. Active bipolar transistors, consisting of heavily and lightly n-doped nanowires crossing a common p-type wire base, exhibit common base and emitter current gains as large as 0.94 and 16, respectively. In addition, p- and n-type nanowires have been used to assemble complementary inverter-like structures. The facile assembly of key electronic device elements from well-defined nanoscale building blocks may represent a step toward a "bottom-up" paradigm for electronics manufacturing.
DOI: 10.1038/nbt1138
2005
Cited 2,280 times
Multiplexed electrical detection of cancer markers with nanowire sensor arrays
DOI: 10.1126/science.1066192
2001
Cited 2,062 times
Logic Gates and Computation from Assembled Nanowire Building Blocks
Miniaturization in electronics through improvements in established "top-down" fabrication techniques is approaching the point where fundamental issues are expected to limit the dramatic increases in computing seen over the past several decades. Here we report a "bottom-up" approach in which functional device elements and element arrays have been assembled from solution through the use of electronically well-defined semiconductor nanowire building blocks. We show that crossed nanowire p-n junctions and junction arrays can be assembled in over 95% yield with controllable electrical characteristics, and in addition, that these junctions can be used to create integrated nanoscale field-effect transistor arrays with nanowires as both the conducting channel and gate electrode. Nanowire junction arrays have been configured as key OR, AND, and NOR logic-gate structures with substantial gain and have been used to implement basic computation.
DOI: 10.1021/nl025875l
2003
Cited 2,058 times
High Performance Silicon Nanowire Field Effect Transistors
Silicon nanowires can be prepared with single-crystal structures, diameters as small as several nanometers and controllable hole and electron doping, and thus represent powerful building blocks for nanoelectronics devices such as field effect transistors. To explore the potential limits of silicon nanowire transistors, we have examined the influence of source-drain contact thermal annealing and surface passivation on key transistor properties. Thermal annealing and passivation of oxide defects using chemical modification were found to increase the average transconductance from 45 to 800 nS and average mobility from 30 to 560 cm2/V·s with peak values of 2000 nS and 1350 cm2/V·s, respectively. The comparison of these results and other key parameters with state-of-the-art planar silicon devices shows substantial advantages for silicon nanowires. The uses of nanowires as building blocks for future nanoelectronics are discussed.
DOI: 10.1021/nl200658a
2011
Cited 1,984 times
Graphene-Wrapped Sulfur Particles as a Rechargeable Lithium–Sulfur Battery Cathode Material with High Capacity and Cycling Stability
We report the synthesis of a graphene-sulfur composite material by wrapping polyethyleneglycol (PEG) coated submicron sulfur particles with mildly oxidized graphene oxide sheets decorated by carbon black nanoparticles. The PEG and graphene coating layers are important to accommodating volume expansion of the coated sulfur particles during discharge, trapping soluble polysulfide intermediates and rendering the sulfur particles electrically conducting. The resulting graphene-sulfur composite showed high and stable specific capacities up to ~600mAh/g over more than 100 cycles, representing a promising cathode material for rechargeable lithium batteries with high energy density.
DOI: 10.1126/science.1062340
2001
Cited 1,733 times
Highly Polarized Photoluminescence and Photodetection from Single Indium Phosphide Nanowires
We have characterized the fundamental photoluminescence (PL) properties of individual, isolated indium phosphide (InP) nanowires to define their potential for optoelectronics. Polarization-sensitive measurements reveal a striking anisotropy in the PL intensity recorded parallel and perpendicular to the long axis of a nanowire. The order-of-magnitude polarization anisotropy was quantitatively explained in terms of the large dielectric contrast between these free-standing nanowires and surrounding environment, as opposed to quantum confinement effects. This intrinsic anisotropy was used to create polarization-sensitive nanoscale photodetectors that may prove useful in integrated photonic circuits, optical switches and interconnects, near-field imaging, and high-resolution detectors.
DOI: 10.1038/nnano.2014.152
2014
Cited 1,558 times
Interconnected hollow carbon nanospheres for stable lithium metal anodes
DOI: 10.1021/nl903949m
2010
Cited 1,409 times
Stretchable, Porous, and Conductive Energy Textiles
Recently there is strong interest in lightweight, flexible, and wearable electronics to meet the technological demands of modern society. Integrated energy storage devices of this type are a key area that is still significantly underdeveloped. Here, we describe wearable power devices using everyday textiles as the platform. With an extremely simple "dipping and drying" process using single-walled carbon nanotube (SWNT) ink, we produced highly conductive textiles with conductivity of 125 S cm(-1) and sheet resistance less than 1 Omega/sq. Such conductive textiles show outstanding flexibility and stretchability and demonstrate strong adhesion between the SWNTs and the textiles of interest. Supercapacitors made from these conductive textiles show high areal capacitance, up to 0.48F/cm(2), and high specific energy. We demonstrate the loading of pseudocapacitor materials into these conductive textiles that leads to a 24-fold increase of the areal capacitance of the device. These highly conductive textiles can provide new design opportunities for wearable electronics and energy storage applications.
DOI: 10.1073/pnas.0908858106
2009
Cited 1,140 times
Highly conductive paper for energy-storage devices
Paper, invented more than 2,000 years ago and widely used today in our everyday lives, is explored in this study as a platform for energy-storage devices by integration with 1D nanomaterials. Here, we show that commercially available paper can be made highly conductive with a sheet resistance as low as 1 ohm per square (Omega/sq) by using simple solution processes to achieve conformal coating of single-walled carbon nanotube (CNT) and silver nanowire films. Compared with plastics, paper substrates can dramatically improve film adhesion, greatly simplify the coating process, and significantly lower the cost. Supercapacitors based on CNT-conductive paper show excellent performance. When only CNT mass is considered, a specific capacitance of 200 F/g, a specific energy of 30-47 Watt-hour/kilogram (Wh/kg), a specific power of 200,000 W/kg, and a stable cycling life over 40,000 cycles are achieved. These values are much better than those of devices on other flat substrates, such as plastics. Even in a case in which the weight of all of the dead components is considered, a specific energy of 7.5 Wh/kg is achieved. In addition, this conductive paper can be used as an excellent lightweight current collector in lithium-ion batteries to replace the existing metallic counterparts. This work suggests that our conductive paper can be a highly scalable and low-cost solution for high-performance energy storage devices.
DOI: 10.1063/1.1363692
2001
Cited 1,110 times
Diameter-controlled synthesis of single-crystal silicon nanowires
Monodisperse silicon nanowires were synthesized by exploiting well-defined gold nanoclusters as catalysts for one-dimensional growth via a vapor–liquid–solid mechanism. Transmission electron microscopy studies of the materials grown from 5, 10, 20, and 30 nm nanocluster catalysts showed that the nanowires had mean diameters of 6, 12, 20, and 31 nm, respectively, and were thus well defined by the nanocluster sizes. High-resolution transmission electron microscopy demonstrated that the nanowires have single-crystal silicon cores sheathed with 1–3 nm of amorphous oxide and that the cores remain highly crystalline for diameters as small as 2 nm.
DOI: 10.1021/nl2026635
2011
Cited 1,068 times
Enhancing the Supercapacitor Performance of Graphene/MnO<sub>2</sub> Nanostructured Electrodes by Conductive Wrapping
MnO2 is considered one of the most promising pseudocapactive materials for high-performance supercapacitors given its high theoretical specific capacitance, low-cost, environmental benignity, and natural abundance. However, MnO2 electrodes often suffer from poor electronic and ionic conductivities, resulting in their limited performance in power density and cycling. Here we developed a "conductive wrapping" method to greatly improve the supercapacitor performance of graphene/MnO2-based nanostructured electrodes. By three-dimensional (3D) conductive wrapping of graphene/MnO2 nanostructures with carbon nanotubes or conducting polymer, specific capacitance of the electrodes (considering total mass of active materials) has substantially increased by ∼20% and ∼45%, respectively, with values as high as ∼380 F/g achieved. Moreover, these ternary composite electrodes have also exhibited excellent cycling performance with >95% capacitance retention over 3000 cycles. This 3D conductive wrapping approach represents an exciting direction for enhancing the device performance of metal oxide-based electrochemical supercapacitors and can be generalized for designing next-generation high-performance energy storage devices.
DOI: 10.1073/pnas.1615837114
2017
Cited 1,036 times
Catalytic oxidation of Li <sub>2</sub> S on the surface of metal sulfides for Li−S batteries
Significance A series of metal sulfides were systematically investigated as polar hosts to reveal the key parameters correlated to the energy barriers and polysulfide adsorption capability in Li−S batteries. The investigation demonstrates that the catalyzing oxidation capability of metal sulfides is critical in reducing the energy barrier and contributing to the remarkably improved battery performance. Density functional theory simulation allows us to identify the mechanism for how binding energy and polysulfides trapping dominate the Li 2 S decomposition process and overall battery performance. The understanding can serve as a general guiding principle for the rational design and screening of advanced materials for high-energy Li−S batteries.
DOI: 10.1038/nnano.2015.112
2015
Cited 1,029 times
Polarization-sensitive broadband photodetector using a black phosphorus vertical p–n junction
The ability to detect light over a broad spectral range is central to practical optoelectronic applications and has been successfully demonstrated with photodetectors of two-dimensional layered crystals such as graphene and MoS2. However, polarization sensitivity within such a photodetector remains elusive. Here, we demonstrate a broadband photodetector using a layered black phosphorus transistor that is polarization-sensitive over a bandwidth from ∼400 nm to 3,750 nm. The polarization sensitivity is due to the strong intrinsic linear dichroism, which arises from the in-plane optical anisotropy of this material. In this transistor geometry, a perpendicular built-in electric field induced by gating can spatially separate the photogenerated electrons and holes in the channel, effectively reducing their recombination rate and thus enhancing the performance for linear dichroism photodetection. The use of anisotropic layered black phosphorus in polarization-sensitive photodetection might provide new functionalities in novel optical and optoelectronic device applications.
DOI: 10.1021/nl901670t
2009
Cited 980 times
Carbon−Silicon Core−Shell Nanowires as High Capacity Electrode for Lithium Ion Batteries
We introduce a novel design of carbon−silicon core−shell nanowires for high power and long life lithium battery electrodes. Amorphous silicon was coated onto carbon nanofibers to form a core−shell structure and the resulted core−shell nanowires showed great performance as anode material. Since carbon has a much smaller capacity compared to silicon, the carbon core experiences less structural stress or damage during lithium cycling and can function as a mechanical support and an efficient electron conducting pathway. These nanowires have a high charge storage capacity of ∼2000 mAh/g and good cycling life. They also have a high Coulmbic efficiency of 90% for the first cycle and 98−99.6% for the following cycles. A full cell composed of LiCoO2 cathode and carbon−silicon core−shell nanowire anode is also demonstrated. Significantly, using these core−shell nanowires we have obtained high mass loading and an area capacity of ∼4 mAh/cm2, which is comparable to commercial battery values.
DOI: 10.1021/nl035162i
2004
Cited 902 times
Controlled Growth and Structures of Molecular-Scale Silicon Nanowires
Single-crystal silicon nanowires with diameters approaching molecular dimensions were synthesized using gold nanocluster-catalyzed 1D growth. High-resolution transmission electron microscopy studies show that silicon nanowires grown with silane reactant in hydrogen are single crystal with little or no visible amorphous oxide down to diameters as small as 3 nm. Structural characterization of a large number of samples shows that the smallest-diameter nanowires grow primarily along the 〈110〉 direction, whereas larger nanowires grow along the 〈111〉 direction. In addition, cross-sectional transmission electron microscopy was used to address the importance of surface energetics in determining the growth direction of the smallest nanowires. The ability to prepare well-defined molecular-scale single-crystal silicon nanowires opens up new opportunities for both fundamental studies and nanodevice applications.
DOI: 10.1021/jp0009305
2000
Cited 882 times
Doping and Electrical Transport in Silicon Nanowires
Single-crystal n-type and p-type silicon nanowires (SiNWs) have been prepared and characterized by electrical transport measurements. Laser catalytic growth was used to introduce controllably either boron or phosphorus dopants during the vapor phase growth of SiNWs. Two-terminal, gate-dependent measurements made on individual boron-doped and phosphorus-doped SiNWs show that these materials behave as p-type and n-type materials, respectively. Estimates of the carrier mobility made from gate-dependent transport measurements are consistent with diffusive transport. In addition, these studies show it is possible to heavily dope SiNWs and approach a metallic regime. Temperature-dependent measurements made on heavily doped SiNWs show no evidence for Coulomb blockade at temperatures down to 4.2 K, and thus testify to the structural and electronic uniformity of the SiNWs. Potential applications of the doped SiNWs are discussed.
DOI: 10.1021/nl015667d
2002
Cited 859 times
Gallium Nitride Nanowire Nanodevices
Field effect transistors (FETs) based on individual GaN nanowires (NWs) have been fabricated. Gate-dependent electrical transport measurements show that the GaN NWs are n-type and that the conductance of NW−FETs can be modulated by more than 3 orders of magnitude. Electron mobilities determined for the GaN NW FETs, which were estimated from the transconductance, were as high as 650 cm2/V·s. These mobilities are comparable to or larger than thin film materials with similar carrier concentration and thus demonstrate the high quality of these NW building blocks and their potential for nanoscale electronics. In addition, p−n junctions have been assembled in high yield from p-type Si, and these n-type GaN NWs and their potential applications are discussed.
DOI: 10.1038/ncomms1563
2011
Cited 830 times
Copper hexacyanoferrate battery electrodes with long cycle life and high power
Short-term transients, including those related to wind and solar sources, present challenges to the electrical grid. Stationary energy storage systems that can operate for many cycles, at high power, with high round-trip energy efficiency, and at low cost are required. Existing energy storage technologies cannot satisfy these requirements. Here we show that crystalline nanoparticles of copper hexacyanoferrate, which has an ultra-low strain open framework structure, can be operated as a battery electrode in inexpensive aqueous electrolytes. After 40,000 deep discharge cycles at a 17 C rate, 83% of the original capacity of copper hexacyanoferrate is retained. Even at a very high cycling rate of 83 C, two thirds of its maximum discharge capacity is observed. At modest current densities, round-trip energy efficiencies of 99% can be achieved. The low-cost, scalable, room-temperature co-precipitation synthesis and excellent electrode performance of copper hexacyanoferrate make it attractive for large-scale energy storage systems.
DOI: 10.1021/nl9034237
2009
Cited 826 times
Nanodome Solar Cells with Efficient Light Management and Self-Cleaning
Here for the first time, we demonstrate novel nanodome solar cells, which have periodic nanoscale modulation for all layers from the bottom substrate, through the active absorber to the top transparent contact. These devices combine many nanophotonic effects to both efficiently reduce reflection and enhance absorption over a broad spectral range. Nanodome solar cells with only a 280 nm thick hydrogenated amorphous silicon (a-Si:H) layer can absorb 94% of the light with wavelengths of 400-800 nm, significantly higher than the 65% absorption of flat film devices. Because of the nearly complete absorption, a very large short-circuit current of 17.5 mA/cm(2) is achieved in our nanodome devices. Excitingly, the light management effects remain efficient over a wide range of incident angles, favorable for real environments with significant diffuse sunlight. We demonstrate nanodome devices with a power efficiency of 5.9%, which is 25% higher than the flat film control. The nanodome structure is not in principle limited to any specific material system and its fabrication is compatible with most solar manufacturing; hence it opens up exciting opportunities for a variety of photovoltaic devices to further improve performance, reduce materials usage, and relieve elemental abundance limitations. Lastly, our nanodome devices when modified with hydrophobic molecules present a nearly superhydrophobic surface and thus enable self-cleaning solar cells.
DOI: 10.1038/nmat3921
2014
Cited 810 times
Light management for photovoltaics using high-index nanostructures
DOI: 10.1038/nenergy.2017.35
2017
Cited 794 times
Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires
DOI: 10.1021/nl501617j
2014
Cited 772 times
Formation of Stable Phosphorus–Carbon Bond for Enhanced Performance in Black Phosphorus Nanoparticle–Graphite Composite Battery Anodes
High specific capacity battery electrode materials have attracted great research attention. Phosphorus as a low-cost abundant material has a high theoretical specific capacity of 2596 mAh/g with most of its capacity at the discharge potential range of 0.4-1.2 V, suitable as anodes. Although numerous research progress have shown other high capacity anodes such as Si, Ge, Sn, and SnO2, there are only a few studies on phosphorus anodes despite its high theoretical capacity. Successful applications of phosphorus anodes have been impeded by rapid capacity fading, mainly caused by large volume change (around 300%) upon lithiation and thus loss of electrical contact. Using the conducting allotrope of phosphorus, "black phosphorus" as starting materials, here we fabricated composites of black phosphorus nanoparticle-graphite by mechanochemical reaction in a high energy mechanical milling process. This process produces phosphorus-carbon bonds, which are stable during lithium insertion/extraction, maintaining excellent electrical connection between phosphorus and carbon. We demonstrated high initial discharge capacity of 2786 mAh·g(-1) at 0.2 C and an excellent cycle life of 100 cycles with 80% capacity retention. High specific discharge capacities are maintained at fast C rates (2270, 1750, 1500, and 1240 mAh·g(-1) at C/5, 1, 2, and 4.5 C, respectively).
DOI: 10.1073/pnas.1518188113
2016
Cited 759 times
Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating
Lithium metal-based battery is considered one of the best energy storage systems due to its high theoretical capacity and lowest anode potential of all. However, dendritic growth and virtually relative infinity volume change during long-term cycling often lead to severe safety hazards and catastrophic failure. Here, a stable lithium-scaffold composite electrode is developed by lithium melt infusion into a 3D porous carbon matrix with "lithiophilic" coating. Lithium is uniformly entrapped on the matrix surface and in the 3D structure. The resulting composite electrode possesses a high conductive surface area and excellent structural stability upon galvanostatic cycling. We showed stable cycling of this composite electrode with small Li plating/stripping overpotential (<90 mV) at a high current density of 3 mA/cm(2) over 80 cycles.
DOI: 10.1021/nl3044508
2013
Cited 700 times
In Situ TEM of Two-Phase Lithiation of Amorphous Silicon Nanospheres
To utilize high-capacity Si anodes in next-generation Li-ion batteries, the physical and chemical transformations during the Li–Si reaction must be better understood. Here, in situ transmission electron microscopy is used to observe the lithiation/delithiation of amorphous Si nanospheres; amorphous Si is an important anode material that has been less studied than crystalline Si. Unexpectedly, the experiments reveal that the first lithiation occurs via a two-phase mechanism, which is contrary to previous understanding and has important consequences for mechanical stress evolution during lithiation. On the basis of kinetics measurements, this behavior is suggested to be due to the rate-limiting effect of Si–Si bond breaking. In addition, the results show that amorphous Si has more favorable kinetics and fracture behavior when reacting with Li than does crystalline Si, making it advantageous to use in battery electrodes. Amorphous spheres up to 870 nm in diameter do not fracture upon lithiation; this is much larger than the 150 nm critical fracture diameter previously identified for crystalline Si spheres.
DOI: 10.1021/nl2023433
2011
Cited 676 times
High-Performance Nanostructured Supercapacitors on a Sponge
A simple and scalable method has been developed to fabricate nanostructured MnO2-carbon nanotube (CNT)-sponge hybrid electrodes. A novel supercapacitor, henceforth referred to as "sponge supercapacitor", has been fabricated using these hybrid electrodes with remarkable performance. A specific capacitance of 1,230 F/g (based on the mass of MnO2) can be reached. Capacitors based on CNT-sponge substrates (without MnO2) can be operated even under a high scan rate of 200 V/s, and they exhibit outstanding cycle performance with only 2% degradation after 100,000 cycles under a scan rate of 10 V/s. The MnO2-CNT-sponge supercapacitors show only 4% of degradation after 10,000 cycles at a charge-discharge specific current of 5 A/g. The specific power and energy of the MnO2-CNT-sponge supercapacitors are high with values of 63 kW/kg and 31 Wh/kg, respectively. The attractive performances exhibited by these sponge supercapacitors make them potentially promising candidates for future energy storage systems.
DOI: 10.1039/c4ta00484a
2014
Cited 625 times
Nanostructured conductive polypyrrole hydrogels as high-performance, flexible supercapacitor electrodes
A spongy polypyrrole based conductive hydrogel with chemically tunable structures and electrochemical characteristics was developed for highly flexible solid-state supercapacitors.
DOI: 10.1021/nl100504q
2010
Cited 608 times
New Nanostructured Li<sub>2</sub>S/Silicon Rechargeable Battery with High Specific Energy
Rechargeable lithium ion batteries are important energy storage devices; however, the specific energy of existing lithium ion batteries is still insufficient for many applications due to the limited specific charge capacity of the electrode materials. The recent development of sulfur/mesoporous carbon nanocomposite cathodes represents a particularly exciting advance, but in full battery cells, sulfur-based cathodes have to be paired with metallic lithium anodes as the lithium source, which can result in serious safety issues. Here we report a novel lithium metal-free battery consisting of a Li(2)S/mesoporous carbon composite cathode and a silicon nanowire anode. This new battery yields a theoretical specific energy of 1550 Wh kg(-1), which is four times that of the theoretical specific energy of existing lithium-ion batteries based on LiCoO(2) cathodes and graphite anodes (approximately 410 Wh kg(-1)). The nanostructured design of both electrodes assists in overcoming the issues associated with using sulfur compounds and silicon in lithium-ion batteries, including poor electrical conductivity, significant structural changes, and volume expansion. We have experimentally realized an initial discharge specific energy of 630 Wh kg(-1) based on the mass of the active electrode materials.
DOI: 10.1038/nenergy.2016.113
2016
Cited 589 times
Scalable synthesis of silicon-nanolayer-embedded graphite for high-energy lithium-ion batteries
DOI: 10.1021/nl204550q
2012
Cited 584 times
Absorption Enhancement in Ultrathin Crystalline Silicon Solar Cells with Antireflection and Light-Trapping Nanocone Gratings
Enhancing the light absorption in ultrathin-film silicon solar cells is important for improving efficiency and reducing cost. We introduce a double-sided grating design, where the front and back surfaces of the cell are separately optimized for antireflection and light trapping, respectively. The optimized structure yields a photocurrent of 34.6 mA/cm(2) at an equivalent thickness of 2 μm, close to the Yablonovitch limit. This approach is applicable to various thicknesses and is robust against metallic loss in the back reflector.
DOI: 10.1126/science.1090899
2003
Cited 569 times
Nanowire Crossbar Arrays as Address Decoders for Integrated Nanosystems
The development of strategies for addressing arrays of nanoscale devices is central to the implementation of integrated nanosystems such as biological sensor arrays and nanocomputers. We report a general approach for addressing based on molecular-level modification of crossed semiconductor nanowire field-effect transistor (cNW-FET) arrays, where selective chemical modification of cross points in the arrays enables NW inputs to turn specific FET array elements on and off. The chemically modified cNW-FET arrays function as decoder circuits, exhibit gain, and allow multiplexing and demultiplexing of information. These results provide a step toward the realization of addressable integrated nanosystems in which signals are restored at the nanoscale.
DOI: 10.1002/adma.201202744
2012
Cited 542 times
Studying the Kinetics of Crystalline Silicon Nanoparticle Lithiation with In Situ Transmission Electron Microscopy
In situ transmission electron microscopy (TEM) is used to study the electrochemical lithiation of high-capacity crystalline Si nanoparticles for use in Li-ion battery anodes. The lithiation reaction slows down as it progresses into the particle interior, and analysis suggests that this behavior is due not to diffusion limitation but instead to the influence of mechanical stress on the driving force for reaction.
DOI: 10.1007/s41918-018-0001-4
2018
Cited 526 times
High-Performance Anode Materials for Rechargeable Lithium-Ion Batteries
DOI: 10.1039/c4ee01377h
2014
Cited 480 times
Improved lithium–sulfur batteries with a conductive coating on the separator to prevent the accumulation of inactive S-related species at the cathode–separator interface
Lithium–sulfur (Li–S) batteries are highly attractive for future generations of portable electronics and electric vehicles due to their high energy density and potentially low cost. In the past decades, various novel electrodes and electrolytes have been tested to improve Li–S battery performance. However, these designs on electrodes and electrolytes have not fully addressed the problem of low cycling stability of Li–S batteries. Here, we show the role of the separator in the capacity decay of the Li–S battery, namely that it can accommodate a large amount of polysulfides inside which then precipitates as a thick layer of inactive S-related species. Using a thin conductive coating on the separator to prevent the formation of the inactive S-related species layer, we show that the specific capacity and cycling stability of the Li–S battery are both improved significantly compared to the battery with a pristine separator. Combining this separator design with a monodisperse sulfur nanoparticle cathode, we show Li–S batteries with a life of over 500 cycles with an initial specific capacity of 1350 mA h g−1 at C/2 and a cycle decay as low as 0.09% per cycle.
DOI: 10.1126/sciadv.1700895
2017
Cited 436 times
A dual-mode textile for human body radiative heating and cooling
Maintaining human body temperature is one of the most basic needs for living, which often consumes a huge amount of energy to keep the ambient temperature constant. To expand the ambient temperature range while maintaining human thermal comfort, the concept of personal thermal management has been recently demonstrated in heating and cooling textiles separately through human body infrared radiation control. Realizing these two opposite functions within the same textile would represent an exciting scientific challenge and a significant technological advancement. We demonstrate a dual-mode textile that can perform both passive radiative heating and cooling using the same piece of textile without any energy input. The dual-mode textile is composed of a bilayer emitter embedded inside an infrared-transparent nanoporous polyethylene (nanoPE) layer. We demonstrate that the asymmetrical characteristics of both emissivity and nanoPE thickness can result in two different heat transfer coefficients and achieve heating when the low-emissivity layer is facing outside and cooling by wearing the textile inside out when the high-emissivity layer is facing outside. This can expand the thermal comfort zone by 6.5°C. Numerical fitting of the data further predicts 14.7°C of comfort zone expansion for dual-mode textiles with large emissivity contrast.
DOI: 10.1021/acs.nanolett.9b04719
2019
Cited 410 times
Theoretical Calculation Guided Design of Single-Atom Catalysts toward Fast Kinetic and Long-Life Li–S Batteries
Lithium–sulfur (Li–S) batteries are promising next-generation energy storage technologies due to their high theoretical energy density, environmental friendliness, and low cost. However, low conductivity of sulfur species, dissolution of polysulfides, poor conversion from sulfur reduction, and lithium sulfide (Li2S) oxidation reactions during discharge–charge processes hinder their practical applications. Herein, under the guidance of density functional theory calculations, we have successfully synthesized large-scale single atom vanadium catalysts seeded on graphene to achieve high sulfur content (80 wt % sulfur), fast kinetic (a capacity of 645 mAh g–1 at 3 C rate), and long-life Li–S batteries. Both forward (sulfur reduction) and reverse reactions (Li2S oxidation) are significantly improved by the single atom catalysts. This finding is confirmed by experimental results and consistent with theoretical calculations. The ability of single metal atoms to effectively trap the dissolved lithium polysulfides (LiPSs) and catalytically convert the LiPSs/Li2S during cycling significantly improved sulfur utilization, rate capability, and cycling life. Our work demonstrates an efficient design pathway for single atom catalysts and provides solutions for the development of high energy/power density Li–S batteries.
DOI: 10.1021/jacs.7b05251
2017
Cited 399 times
Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability
Significant increases in the energy density of batteries must be achieved by exploring new materials and cell configurations. Lithium metal and lithiated silicon are two promising high-capacity anode materials. Unfortunately, both of these anodes require a reliable passivating layer to survive the serious environmental corrosion during handling and cycling. Here we developed a surface fluorination process to form a homogeneous and dense LiF coating on reactive anode materials, with in situ generated fluorine gas, by using a fluoropolymer, CYTOP, as the precursor. The process is effectively a "reaction in the beaker", avoiding direct handling of highly toxic fluorine gas. For lithium metal, this LiF coating serves as a chemically stable and mechanically strong interphase, which minimizes the corrosion reaction with carbonate electrolytes and suppresses dendrite formation, enabling dendrite-free and stable cycling over 300 cycles with current densities up to 5 mA/cm2. Lithiated silicon can serve as either a pre-lithiation additive for existing lithium-ion batteries or a replacement for lithium metal in Li-O2 and Li-S batteries. However, lithiated silicon reacts vigorously with the standard slurry solvent N-methyl-2-pyrrolidinone (NMP), indicating it is not compatible with the real battery fabrication process. With the protection of crystalline and dense LiF coating, LixSi can be processed in anhydrous NMP with a high capacity of 2504 mAh/g. With low solubility of LiF in water, this protection layer also allows LixSi to be stable in humid air (∼40% relative humidity). Therefore, this facile surface fluorination process brings huge benefit to both the existing lithium-ion batteries and next-generation lithium metal batteries.
DOI: 10.1021/nl300713x
2012
Cited 398 times
Hybrid Silicon Nanocone–Polymer Solar Cells
Recently, hybrid Si/organic solar cells have been studied for low-cost Si photovoltaic devices because the Schottky junction between the Si and organic material can be formed by solution processes at a low temperature. In this study, we demonstrate a hybrid solar cell composed of Si nanocones and conductive polymer. The optimal nanocone structure with an aspect ratio (height/diameter of a nanocone) less than two allowed for conformal polymer surface coverage via spin-coating while also providing both excellent antireflection and light trapping properties. The uniform heterojunction over the nanocones with enhanced light absorption resulted in a power conversion efficiency above 11%. Based on our simulation study, the optimal nanocone structures for a 10 μm thick Si solar cell can achieve a short-circuit current density, up to 39.1 mA/cm2, which is very close to the theoretical limit. With very thin material and inexpensive processing, hybrid Si nanocone/polymer solar cells are promising as an economically viable alternative energy solution.
DOI: 10.1021/acs.nanolett.7b00221
2017
Cited 394 times
Solid-State Lithium–Sulfur Batteries Operated at 37 °C with Composites of Nanostructured Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub>/Carbon Foam and Polymer
An all solid-state lithium-ion battery with high energy density and high safety is a promising solution for a next-generation energy storage system. High interface resistance of the electrodes and poor ion conductivity of solid-state electrolytes are two main challenges for solid-state batteries, which require operation at elevated temperatures of 60–90 °C. Herein, we report the facile synthesis of Al3+/Nb5+ codoped cubic Li7La3Zr2O12 (LLZO) nanoparticles and LLZO nanoparticle-decorated porous carbon foam (LLZO@C) by the one-step Pechini sol–gel method. The LLZO nanoparticle-filled poly(ethylene oxide) electrolyte shows improved conductivity compared with filler-free samples. The sulfur composite cathode based on LLZO@C can deliver an attractive specific capacity of >900 mAh g–1 at the human body temperature 37 °C and a high capacity of 1210 and 1556 mAh g–1 at 50 and 70 °C, respectively. In addition, the solid-state Li–S batteries exhibit high Coulombic efficiency and show remarkably stable cycling performance.
DOI: 10.1002/adma.201802152
2018
Cited 393 times
Spectrally Selective Nanocomposite Textile for Outdoor Personal Cooling
Abstract Outdoor heat stress poses a serious public health threat and curtails industrial labor supply and productivity, thus adversely impacting the wellness and economy of the entire society. With climate change, there will be more intense and frequent heat waves that further present a grand challenge for sustainability. However, an efficient and economical method that can provide localized outdoor cooling of the human body without intensive energy input is lacking. Here, a novel spectrally selective nanocomposite textile for radiative outdoor cooling using zinc oxide nanoparticle–embedded polyethylene is demonstrated. By reflecting more than 90% solar irradiance and selectively transmitting out human body thermal radiation, this textile can enable simulated skin to avoid overheating by 5–13 °C compared to normal textile like cotton under peak daylight condition. Owing to its superior passive cooling capability and compatibility with large‐scale production, this radiative outdoor cooling textile is promising to widely benefit the sustainability of society in many aspects spanning from health to economy.
DOI: 10.1038/s41893-018-0023-2
2018
Cited 388 times
Nanoporous polyethylene microfibres for large-scale radiative cooling fabric
DOI: 10.1038/s41560-017-0014-y
2017
Cited 376 times
High-performance sodium–organic battery by realizing four-sodium storage in disodium rhodizonate
Sodium-ion batteries (SIBs) for grid-scale applications need active materials that combine a high energy density with sustainability. Given the high theoretical specific capacity 501 mAh g−1, and Earth abundance of disodium rhodizonate (Na2C6O6), it is one of the most promising cathodes for SIBs. However, substantially lower reversible capacities have been obtained compared with the theoretical value and the understanding of this discrepancy has been limited. Here, we reveal that irreversible phase transformation of Na2C6O6 during cycling is the origin of the deteriorating redox activity of Na2C6O6. The active-particle size and electrolyte conditions were identified as key factors to decrease the activation barrier of the phase transformation during desodiation. On the basis of this understanding, we achieved four-sodium storage in a Na2C6O6 electrode with a reversible capacity of 484 mAh g−1, an energy density of 726 Wh kg−1 cathode, an energy efficiency above 87% and a good cycle retention. Sodium-ion batteries are a cost-effective alternative to lithium-ion for large-scale energy storage. Here Bao et al. develop a cathode based on biomass-derived ionic crystals that enables a four-sodium ion storage mechanism leading to exceptionally high specific capacity and energy density.
DOI: 10.1038/ncomms4943
2014
Cited 374 times
Improving lithium–sulphur batteries through spatial control of sulphur species deposition on a hybrid electrode surface
Lithium-sulphur batteries are attractive owing to their high theoretical energy density and reasonable kinetics. Despite the success of trapping soluble polysulphides in a matrix with high surface area, spatial control of solid-state sulphur and lithium sulphide species deposition as a critical aspect has not been demonstrated. Herein, we show a clear visual evidence that these solid species deposit preferentially onto tin-doped indium oxide instead of carbon during electrochemical charge/discharge of soluble polysuphides. To incorporate this concept of spatial control into more practical battery electrodes, we further prepare carbon nanofibers with tin-doped indium oxide nanoparticles decorating the surface as hybrid three-dimensional electrodes to maximize the number of deposition sites. With 12.5 μl of 5 M Li2S8 as the catholyte and a rate of C/5, we can reach the theoretical limit of Li2S8 capacity ~\n1,470 mAh g(-1) (sulphur weight) under the loading of hybrid electrode only at 4.3 mg cm(-2).
DOI: 10.1021/nl062883j
2007
Cited 370 times
Fast, Completely Reversible Li Insertion in Vanadium Pentoxide Nanoribbons
Layered-structure nanoribbons with efficient electron transport and short lithium ion insertion lengths are promising candidates for Li battery applications. Here we studied at the single nanostructure level the chemical, structural, and electrical transformations of V2O5 nanoribbons. We found that transformation of V2O5 into the omega-Li3V2O5 phase depends not only on the width but also the thickness of the nanoribbons. Transformation can take place within 10 s in thin nanoribbons, suggesting a Li diffusion constant 3 orders of magnitude faster than in bulk materials, resulting in a significant increase in battery power density (360 C power rate). For the first time, complete delithiation of omega-Li3V2O5 back to the single-crystalline, pristine V2O5 nanoribbon was observed, indicating a 30% higher energy density. These new observations are attributed to the ability of facile strain relaxation and phase transformation at the nanoscale. In addition, efficient electronic transport can be maintained to charge a Li3V2O5 nanoribbon within less than 5 s. These exciting nanosize effects can be exploited to fabricate high-performance Li batteries for applications in electric and hybrid electric vehicles.
DOI: 10.1021/jacs.8b06020
2018
Cited 354 times
Stabilization of Hexaaminobenzene in a 2D Conductive Metal–Organic Framework for High Power Sodium Storage
Redox-active organic materials have gained growing attention as electrodes of rechargeable batteries. However, their key limitations are the low electronic conductivity and limited chemical and structural stability under redox conditions. Herein, we report a new cobalt-based 2D conductive metal–organic framework (MOF), Co-HAB, having stable, accessible, dense active sites for high-power energy storage device through conjugative coordination between a redox-active linker, hexaaminobenzene (HAB), and a Co(II) center. Given the exceptional capability of Co-HAB for stabilizing reactive HAB, a reversible three-electron redox reaction per HAB was successfully demonstrated for the first time, thereby presenting a promising new electrode material for sodium-ion storage. Specifically, through synthetic tunability of Co-HAB, the bulk electrical conductivity of 1.57 S cm–1 was achieved, enabling an extremely high rate capability, delivering 214 mAh g–1 within 7 min or 152 mAh g–1 in 45 s. Meanwhile, an almost linear increase of the areal capacity upon increasing active mass loading up to 9.6 mg cm–2 was obtained, demonstrating 2.6 mAh cm–2 with a trace amount of conducting agent.
DOI: 10.1063/1.2988893
2008
Cited 342 times
Wafer-scale silicon nanopillars and nanocones by Langmuir–Blodgett assembly and etching
We have developed a method combining Langmuir–Blodgett assembly and reactive ion etching to fabricate nanopillars with uniform coverage over an entire 4 inch wafer. We demonstrated precise control over the diameter and separation between the nanopillars ranging from 60 to 600 nm. We can also change the shape of the pillars from having vertical to tapered sidewalls with sharp tips exhibiting a radius of curvature of 5 nm. This method opens up many possible opportunities in nanoimprinting, solar cells, batteries, and scanning probes.
DOI: 10.1038/s41560-018-0147-7
2018
Cited 342 times
A manganese–hydrogen battery with potential for grid-scale energy storage
Batteries including lithium-ion, lead–acid, redox-flow and liquid-metal batteries show promise for grid-scale storage, but they are still far from meeting the grid's storage needs such as low cost, long cycle life, reliable safety and reasonable energy density for cost and footprint reduction. Here, we report a rechargeable manganese–hydrogen battery, where the cathode is cycled between soluble Mn2+ and solid MnO2 with a two-electron reaction, and the anode is cycled between H2 gas and H2O through well-known catalytic reactions of hydrogen evolution and oxidation. This battery chemistry exhibits a discharge voltage of ~1.3 V, a rate capability of 100 mA cm−2 (36 s of discharge) and a lifetime of more than 10,000 cycles without decay. We achieve a gravimetric energy density of ~139 Wh kg−1 (volumetric energy density of ~210 Wh l−1), with the theoretical gravimetric energy density of ~174 Wh kg−1 (volumetric energy density of ~263 Wh l−1) in a 4 M MnSO4 electrolyte. The manganese–hydrogen battery involves low-cost abundant materials and has the potential to be scaled up for large-scale energy storage. There is an intensive effort to develop stationary energy storage technologies. Now, Yi Cui and colleagues develop a Mn–H battery that functions with redox couples of Mn2+/MnO2 and H2/H2O, and demonstrate its potential for grid-scale storage.
DOI: 10.1021/acsnano.6b06797
2016
Cited 318 times
Improved Lithium Ionic Conductivity in Composite Polymer Electrolytes with Oxide-Ion Conducting Nanowires
Solid Li-ion electrolytes used in all-solid-state lithium-ion batteries (LIBs) are being considered to replace conventional liquid electrolytes that have leakage, flammability, and poor chemical stability issues, which represents one major challenge and opportunity for next-generation high-energy-density batteries. However, the low mobility of lithium ions in solid electrolytes limits their practical applications. Here, we report a solid composite polymer electrolyte with Y2O3-doped ZrO2 (YSZ) nanowires that are enriched with positive-charged oxygen vacancies. The morphologies and ionic conductivities have been studied systemically according to concentration of Y2O3 dopant in the nanowires. In comparison to the conventional filler-free electrolyte with a conductivity of 3.62 × 10-7 S cm-1, the composite polymer electrolytes with the YSZ nanowires show much higher ionic conductivity. It indicates that incorporation of 7 mol % of Y2O3-doped ZrO2 nanowires results in the highest ionic conductivity of 1.07 × 10-5 S cm-1 at 30 °C. This conductivity enhancement originates from the positive-charged oxygen vacancies on the surfaces of the nanowires that could associate with anions and then release more Li ions. Our work demonstrates a composite polymer electrolyte with oxygen-ion conductive nanowires that could address the challenges of all-solid-state LIBs.
DOI: 10.1038/ncomms6193
2014
Cited 312 times
Improving battery safety by early detection of internal shorting with a bifunctional separator
Lithium-based rechargeable batteries have been widely used in portable electronics and show great promise for emerging applications in transportation and wind-solar-grid energy storage, although their safety remains a practical concern. Failures in the form of fire and explosion can be initiated by internal short circuits associated with lithium dendrite formation during cycling. Here we report a new strategy for improving safety by designing a smart battery that allows internal battery health to be monitored in situ. Specifically, we achieve early detection of lithium dendrites inside batteries through a bifunctional separator, which offers a third sensing terminal in addition to the cathode and anode. The sensing terminal provides unique signals in the form of a pronounced voltage change, indicating imminent penetration of dendrites through the separator. This detection mechanism is highly sensitive, accurate and activated well in advance of shorting and can be applied to many types of batteries for improved safety.
DOI: 10.1021/acs.chemrev.9b00326
2019
Cited 312 times
Nanowires for Electrochemical Energy Storage
Nanomaterials provide many desirable properties for electrochemical energy storage devices due to their nanoscale size effect, which could be significantly different from bulk or micron-sized materials. Particularly, confined dimensions play important roles in determining the properties of nanomaterials, such as the kinetics of ion diffusion, the magnitude of strain/stress, and the utilization of active materials. Nanowires, as one of the representative one-dimensional nanomaterials, have great capability for realizing a variety of applications in the fields of energy storage since they could maintain electron transport along the long axis and have a confinement effect across the diameter. In this review, we give a systematic overview of the state-of-the-art research progress on nanowires for electrochemical energy storage, from rational design and synthesis, in situ structural characterizations, to several important applications in energy storage including lithium-ion batteries, lithium-sulfur batteries, sodium-ion batteries, and supercapacitors. The problems and limitations in electrochemical energy storage and the advantages in utilizing nanowires to address the issues and improve the device performance are pointed out. At the end, we also discuss the challenges and demonstrate the prospective for the future development of advanced nanowire-based energy storage devices.
DOI: 10.1021/jacs.8b06047
2018
Cited 309 times
Effects of Polymer Coatings on Electrodeposited Lithium Metal
The electrodeposition of lithium metal is a key process in next-generation, high energy density storage devices. However, the high reactivity of the lithium metal causes short cycling lifetimes and dendrite growth that can pose a serious safety issue. Recently, a number of approaches have been pursued to stabilize the lithium metal–electrolyte interface, including soft polymeric coatings that have shown the ability to enable high-rate and high-capacity lithium metal cycling, but a clear understanding of how to design and modify these coatings has not yet been established. In this work, we studied the effects of several polymers with systematically varied chemical and mechanical properties as coatings on the lithium metal anode. By examining the early stages of lithium metal deposition, we determine that the morphology of the lithium particles is strongly influenced by the chemistry of the polymer coating. We have identified polymer dielectric constant and surface energy as two key descriptors of the lithium deposit size. Low surface energy polymers were found to promote larger deposits with smaller surface areas. This may be explained by a reduced interaction between the coating and the lithium surface and thus an increase in the interfacial energy. On the other hand, high dielectric constant polymers were found to increase the exchange current and gave larger lithium deposits due to the decreased overpotentials at a fixed current density. We also observed that the thickness of the polymer coating should be optimized for each individual polymer. Furthermore, polymer reactivity was found to strongly influence the Coulombic efficiency. Overall, this work offers new fundamental insights into lithium electrodeposition processes and provides direction for the design of new polymer coatings to better stabilize the lithium metal anode.
DOI: 10.1016/j.joule.2018.08.004
2018
Cited 296 times
Correlating Structure and Function of Battery Interphases at Atomic Resolution Using Cryoelectron Microscopy
Battery decay and failure depend strongly on the solid electrolyte interphase (SEI), a surface corrosion layer that forms on the surface of all battery electrodes. Recently, we revealed the atomic structure of these reactive and sensitive battery materials and their SEIs using cryoelectron microscopy (cryo-EM). However, the SEI nanostructure's fundamental role and effect on battery performance remain unclear. Here, we use cryo-EM to discover the function of two distinct SEI nanostructures (i.e., mosaic and multilayer) and correlate their stark effects with Li metal battery performance. We identify fluctuations in crystalline grain distribution within the SEI as the critical feature differentiating the mosaic SEI from the multilayer SEI, resulting in their distinct electrochemical stripping mechanisms. Whereas localized Li dissolution occurs quickly through regions of high crystallinity in the mosaic SEI, uniform Li stripping is observed for the more ordered multilayer SEIs, which reduces Li loss during battery cycling by a factor of three. This dramatic performance enhancement from a subtle change in SEI nanostructure highlights the importance of cryo-EM studies in revealing crucial failure modes of high-energy batteries at the nanoscale.
DOI: 10.1039/c2ee21437g
2012
Cited 270 times
Improving the cycling stability of silicon nanowire anodes with conducting polymer coatings
For silicon nanowires (Si NWs) to be used as a successful high capacity lithium-ion battery anode material, improvements in cycling stability are required. Here we show that a conductive polymer surface coating on the Si NWs improves cycling stability; coating with PEDOT causes the capacity retention after 100 charge–discharge cycles to increase from 30% to 80% over bare NWs. The improvement in cycling stability is attributed to the conductive coating maintaining the mechanical integrity of the cycled Si material, along with preserving electrical connections between NWs that would otherwise have become electrically isolated during volume changes.
DOI: 10.1038/nenergy.2015.9
2016
Cited 270 times
Fast and reversible thermoresponsive polymer switching materials for safer batteries
DOI: 10.1038/s41467-020-14550-3
2020
Cited 269 times
Mechanical rolling formation of interpenetrated lithium metal/lithium tin alloy foil for ultrahigh-rate battery anode
Abstract To achieve good rate capability of lithium metal anodes for high-energy-density batteries, one fundamental challenge is the slow lithium diffusion at the interface. Here we report an interpenetrated, three-dimensional lithium metal/lithium tin alloy nanocomposite foil realized by a simple calendering and folding process of lithium and tin foils, and spontaneous alloying reactions. The strong affinity between the metallic lithium and lithium tin alloy as mixed electronic and ionic conducting networks, and their abundant interfaces enable ultrafast charger diffusion across the entire electrode. We demonstrate that a lithium/lithium tin alloy foil electrode sustains stable lithium stripping/plating under 30 mA cm −2 and 5 mAh cm −2 with a very low overpotential of 20 mV for 200 cycles in a commercial carbonate electrolyte. Cycled under 6 C (6.6 mA cm −2 ), a 1.0 mAh cm −2 LiNi 0.6 Co 0.2 Mn 0.2 O 2 electrode maintains a substantial 74% of its capacity by pairing with such anode.
DOI: 10.1002/anie.201103163
2011
Cited 262 times
LiMn<sub>1−<i>x</i></sub>Fe<sub><i>x</i></sub>PO<sub>4</sub> Nanorods Grown on Graphene Sheets for Ultrahigh‐Rate‐Performance Lithium Ion Batteries
A two-step solution-phase synthesis led to LiMn0.75Fe0.25PO4 nanorods grown on graphene with superior electrical conductivity (see picture; rmGO=reduced mildly oxidized graphene oxide). The nanorod morphology is ideal for fast Li+ diffusion, with the diffusion path along the short radial direction (20–30 nm) of the nanorods. An ultrafast discharge performance for this hybrid cathode material is thus achieved. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
DOI: 10.18632/oncotarget.10234
2016
Cited 262 times
CRISPR-dCas9 mediated TET1 targeting for selective DNA demethylation at <i>BRCA1</i> promoter
DNA hypermethylation at the promoter of tumour-suppressor genes is tightly correlated with their transcriptional repression and recognized as the hallmark of majority of cancers. Epigenetic silencing of tumour suppressor genes impairs their cellular functions and activates a cascade of events driving cell transformation and cancer progression. Here, we examine site-specific and spatiotemporal alteration in DNA methylation at a target region in BRCA1 gene promoter, a model tumour suppressor gene. We have developed a programmable CRISPR-Cas9 based demethylase tool containing the deactivated Cas9 (dCas9) fused to the catalytic domain (CD) of Ten-Eleven Translocation (TET) dioxygenase1 (TET1CD). The fusion protein selectively demethylates targeted regions within BRCA1 promoter as directed by the designed single-guide RNAs (sgRNA), leading to the transcriptional up-regulation of the gene. We also noticed the increment in 5-hydroxymethylation content (5-hmC) at the target DNA site undergoing the most profound demethylation. It confirms the catalytic activity of TET1 in TET1-dCas9 fusion proteins-mediated demethylation at these target sequences. The modular design of the fusion constructs presented here allows for the selective substitution of other chromatin or DNA modifying enzymes and for loci-specific targeting to uncover epigenetic regulatory pathways at gene promoters and other selected genomic regions.
DOI: 10.1002/adma.201505299
2016
Cited 248 times
3D Porous Sponge‐Inspired Electrode for Stretchable Lithium‐Ion Batteries
A stretchable Li4Ti5O12 anode and a LiFePO4 cathode with 80% stretchability are prepared using a 3D interconnected porous polydimethylsiloxane sponge based on sugar cubes. 82% and 91% capacity retention for anode and cathode are achieved after 500 stretch–release cycles. Slight capacity decay of 6% in the battery using the electrode in stretched state is observed. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
DOI: 10.1038/nnano.2017.98
2017
Cited 246 times
Nanoscale manipulation of membrane curvature for probing endocytosis in live cells
Clathrin-mediated endocytosis (CME) involves nanoscale bending and inward budding of the plasma membrane, by which cells regulate both the distribution of membrane proteins and the entry of extracellular species. Extensive studies have shown that CME proteins actively modulate the plasma membrane curvature. However, the reciprocal regulation of how the plasma membrane curvature affects the activities of endocytic proteins is much less explored, despite studies suggesting that membrane curvature itself can trigger biochemical reactions. This gap in our understanding is largely due to technical challenges in precisely controlling the membrane curvature in live cells. In this work, we use patterned nanostructures to generate well-defined membrane curvatures ranging from +50 nm to -500 nm radius of curvature. We find that the positively curved membranes are CME hotspots, and that key CME proteins, clathrin and dynamin, show a strong preference towards positive membrane curvatures with a radius <200 nm. Of ten CME-related proteins we examined, all show preferences for positively curved membrane. In contrast, other membrane-associated proteins and non-CME endocytic protein caveolin1 show no such curvature preference. Therefore, nanostructured substrates constitute a novel tool for investigating curvature-dependent processes in live cells.
DOI: 10.1021/nl100258p
2010
Cited 235 times
Stepwise Nanopore Evolution in One-Dimensional Nanostructures
We report that established simple lithium (Li) ion battery cycles can be used to produce nanopores inside various useful one-dimensional (1D) nanostructures such as zinc oxide, silicon, and silver nanowires. Moreover, porosities of these 1D nanomaterials can be controlled in a stepwise manner by the number of Li-battery cycles. Subsequent pore characterization at the end of each cycle allows us to obtain detailed snapshots of the distinct pore evolution properties in each material due to their different atomic diffusion rates and types of chemical bonds. Also, this stepwise characterization led us to the first observation of pore size increases during cycling, which can be interpreted as a similar phenomenon to Ostwald ripening in analogous nanoparticle cases. Finally, we take advantage of the unique combination of nanoporosity and 1D materials and demonstrate nanoporous silicon nanowires (poSiNWs) as excellent supercapacitor (SC) electrodes in high power operations compared to existing devices with activated carbon.
DOI: 10.1002/aenm.201100261
2011
Cited 234 times
Lithium‐Ion Textile Batteries with Large Areal Mass Loading
We integrate Li-ion battery electrode materials into a 3D porous textile conductor by using a simple process. When compared to flat metal current collectors, our 3D porous textile conductor not only greatly facilitates the ability for a high active material mass loading on the battery electrode but also leads to better device performance.
DOI: 10.1021/jacs.9b11056
2020
Cited 234 times
A New Class of Ionically Conducting Fluorinated Ether Electrolytes with High Electrochemical Stability
Increasing battery energy density is greatly desired for applications such as portable electronics and transportation. However, many next-generation batteries are limited by electrolyte selection because high ionic conductivity and poor electrochemical stability are typically observed in most electrolytes. For example, ether-based electrolytes have high ionic conductivity but are oxidatively unstable above 4 V, which prevents the use of high-voltage cathodes that promise higher energy densities. In contrast, hydrofluoroethers (HFEs) have high oxidative stability but do not dissolve lithium salt. In this work, we synthesize a new class of fluorinated ether electrolytes that combine the oxidative stability of HFEs with the ionic conductivity of ethers in a single compound. We show that conductivities of up to 2.7 × 10-4 S/cm (at 30 °C) can be obtained with oxidative stability up to 5.6 V. The compounds also show higher lithium transference numbers compared to typical ethers. Furthermore, we use nuclear magnetic resonance (NMR) and molecular dynamics (MD) to study their ionic transport behavior and ion solvation environment, respectively. Finally, we demonstrate that this new class of electrolytes can be used with a Ni-rich layered cathode (NMC 811) to obtain over 100 cycles at a C/5 rate. The design of new molecules with high ionic conductivity and high electrochemical stability is a novel approach for the rational design of next-generation batteries.
DOI: 10.1002/aenm.201703138
2018
Cited 225 times
Ionically Conductive Self‐Healing Binder for Low Cost Si Microparticles Anodes in Li‐Ion Batteries
Abstract A self‐healing polymer (SHP) with abundant hydrogen bonds, appropriate viscoelasticity, and stretchability is a promising binder to improve cycle performance of Si microparticle anodes in lithium (Li) ion batteries. Besides high capacity and long cycle life, efficient rate performance is strongly desirable for practical Si anode implementation. Here, polyethylene glycol (PEG) groups are incorporated into the SHP, facilitating Li ionic conduction within the binder. The concept of the SHP‐PEG binder involves improving the interface between Si microparticles and electrolytes after cycling based on the combination of self‐healing ability and fast Li ionic conduction. Through the systematic study of mixing PEG Mw and ratio, the polymeric binder combining SHP and PEG with M w 750 in an optimal ratio of 60:40 (mol%) achieves a high discharging capacity of ≈2600 mA h g −1 , reasonable rate performance especially when &gt;1C and maintains 80% of their initial capacity even after ≈150 cycles at 0.5C. The described concept for the polymeric binder, embedding both self‐healing ability and high Li ionic conductivity, should be equally useful for next generation batteries utilizing high capacity materials which suffer from huge volume change during cycling.
DOI: 10.1002/aenm.201100056
2011
Cited 224 times
Silicon–Carbon Nanotube Coaxial Sponge as Li‐Ion Anodes with High Areal Capacity
Highly porous, conductive Si-CNT sponge-like structures with a large areal mass loading are demonstrated as effective Li-ion battery anode materials. Nanopore formation and growth in the Si shell has been identified as the primary failure mode of the Si-CNT sponge anode, and the formation of such nanopores can be minimized by tuning the cutoff voltages. In conjunction with experiments, a theoretical analysis was carried out to explain the pore formation mechanism. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
DOI: 10.1016/j.joule.2019.03.015
2019
Cited 224 times
Temperature Regulation in Colored Infrared-Transparent Polyethylene Textiles
Effectively regulating heat flow between the human body and its environment not only increases thermal comfort but also presents a novel and potentially cost-effective approach to reducing building energy consumption. Infrared property-engineered textiles have been shown to passively regulate radiative heat dissipation for effective cooling and warming of the human body. However, a lack of dyes that can tune the textile color without compromising the infrared properties remains a major impediment to textile commercialization. Here, we report a new strategy utilizing inorganic nanoparticles as a coloring component for scalable brightly colored, infrared-transparent textiles. The as-fabricated composite textiles not only show a high infrared transparency of ∼80% and a passive cooling effect of ∼1.6°C–1.8°C but also exhibit intense visible colors with good stability against washing. This facile coloration approach will promote the commercialization of radiative cooling textiles in temperature-regulating wearable applications for effective energy savings.
DOI: 10.1021/jacs.1c09006
2021
Cited 217 times
Steric Effect Tuned Ion Solvation Enabling Stable Cycling of High-Voltage Lithium Metal Battery
1,2-Dimethoxyethane (DME) is a common electrolyte solvent for lithium metal batteries. Various DME-based electrolyte designs have improved long-term cyclability of high-voltage full cells. However, insufficient Coulombic efficiency at the Li anode and poor high-voltage stability remain a challenge for DME electrolytes. Here, we report a molecular design principle that utilizes a steric hindrance effect to tune the solvation structures of Li+ ions. We hypothesized that by substituting the methoxy groups on DME with larger-sized ethoxy groups, the resulting 1,2-diethoxyethane (DEE) should have a weaker solvation ability and consequently more anion-rich inner solvation shells, both of which enhance interfacial stability at the cathode and anode. Experimental and computational evidence indicates such steric-effect-based design leads to an appreciable improvement in electrochemical stability of lithium bis(fluorosulfonyl)imide (LiFSI)/DEE electrolytes. Under stringent full-cell conditions of 4.8 mAh cm-2 NMC811, 50 μm thin Li, and high cutoff voltage at 4.4 V, 4 M LiFSI/DEE enabled 182 cycles until 80% capacity retention while 4 M LiFSI/DME only achieved 94 cycles. This work points out a promising path toward the molecular design of non-fluorinated ether-based electrolyte solvents for practical high-voltage Li metal batteries.
DOI: 10.1126/science.aax2656
2021
Cited 214 times
Expansion sequencing: Spatially precise in situ transcriptomics in intact biological systems
Methods for highly multiplexed RNA imaging are limited in spatial resolution and thus in their ability to localize transcripts to nanoscale and subcellular compartments. We adapt expansion microscopy, which physically expands biological specimens, for long-read untargeted and targeted in situ RNA sequencing. We applied untargeted expansion sequencing (ExSeq) to the mouse brain, which yielded the readout of thousands of genes, including splice variants. Targeted ExSeq yielded nanoscale-resolution maps of RNAs throughout dendrites and spines in the neurons of the mouse hippocampus, revealing patterns across multiple cell types, layer-specific cell types across the mouse visual cortex, and the organization and position-dependent states of tumor and immune cells in a human metastatic breast cancer biopsy. Thus, ExSeq enables highly multiplexed mapping of RNAs from nanoscale to system scale.
DOI: 10.1002/adma.201706745
2018
Cited 213 times
Wood‐Inspired High‐Performance Ultrathick Bulk Battery Electrodes
Abstract Ultrathick electrode design is a promising strategy to enhance the specific energy of Li‐ion batteries (LIBs) without changing the underlying materials chemistry. However, the low Li‐ion conductivity caused by ultralong Li‐ion transport pathway in traditional random microstructured electrode heavily deteriorates the rate performance of ultrathick electrodes. Herein, inspired by the vertical microchannels in natural wood as the highway for water transport, the microstructures of wood are successfully duplicated into ultrathick bulk LiCoO 2 (LCO) cathode via a sol–gel process to achieve the high areal capacity and excellent rate capability. The X‐ray‐based microtomography demonstrates that the uniform microchannels are built up throughout the whole wood‐templated LCO cathode bringing in 1.5 times lower of tortuosity and ≈2 times higher of Li‐ion conductivity compared to that of random structured LCO cathode. The fabricated wood‐inspired LCO cathode delivers high areal capacity up to 22.7 mAh cm −2 (five times of the existing electrode) and achieves the dynamic stress test at such high areal capacity for the first time. The reported wood‐inspired design will open a new avenue to adopt natural hierarchical structures to improve the performance of LIBs.
DOI: 10.1021/nl401729r
2013
Cited 209 times
Crab Shells as Sustainable Templates from Nature for Nanostructured Battery Electrodes
Rational nanostructure design has been a promising route to address critical materials issues for enabling next-generation high capacity lithium ion batteries for portable electronics, vehicle electrification, and grid-scale storage. However, synthesis of functional nanostructures often involves expensive starting materials and elaborate processing, both of which present a challenge for successful implementation in low-cost applications. In seeking a sustainable and cost-effective route to prepare nanostructured battery electrode materials, we are inspired by the diversity of natural materials. Here, we show that crab shells with the unique Bouligand structure consisting of highly mineralized chitin-protein fibers can be used as biotemplates to fabricate hollow carbon nanofibers; these fibers can then be used to encapsulate sulfur and silicon to form cathodes and anodes for Li-ion batteries. The resulting nanostructured electrodes show high specific capacities (1230 mAh/g for sulfur and 3060 mAh/g for silicon) and excellent cycling performance (up to 200 cycles with 60% and 95% capacity retention, respectively). Since crab shells are readily available due to the 0.5 million tons produced annually as a byproduct of crab consumption, their use as a sustainable and low-cost nanotemplate represents an exciting direction for nanostructured battery materials.
DOI: 10.1038/s43018-020-0026-6
2020
Cited 209 times
Imaging mass cytometry and multiplatform genomics define the phenogenomic landscape of breast cancer
Genomic alterations shape cell phenotypes and the structure of tumor ecosystems in poorly defined ways. To investigate these relationships, we used imaging mass cytometry to quantify the expression of 37 proteins with subcellular spatial resolution in 483 tumors from the METABRIC cohort. Single-cell analysis revealed cell phenotypes spanning epithelial, stromal and immune types. Distinct combinations of cell phenotypes and cell–cell interactions were associated with genomic subtypes of breast cancer. Epithelial luminal cell phenotypes separated into those predominantly impacted by mutations and those affected by copy number aberrations. Several features of tumor ecosystems, including cellular neighborhoods, were linked to prognosis, illustrating their clinical relevance. In summary, systematic analysis of single-cell phenotypic and spatial correlates of genomic alterations in cancer revealed how genomes shape both the composition and architecture of breast tumor ecosystems and will enable greater understanding of the phenotypic impact of genomic alterations. Bodenmiller and colleagues pair imaging mass cytometry with data from the METABRIC cohort to define single-cell phenotypic and genomic features of breast cancer with spatial context, finding associations with breast cancer subtypes and prognosis.
DOI: 10.1021/acsenergylett.0c00194
2020
Cited 206 times
Resolving Nanoscopic and Mesoscopic Heterogeneity of Fluorinated Species in Battery Solid-Electrolyte Interphases by Cryogenic Electron Microscopy
The stability of lithium batteries is tied to the physicochemical properties of the solid-electrolyte interphase (SEI). Owing to the difficulty in characterizing this sensitive interphase, the nanoscale distribution of SEI components is poorly understood. Here, we use cryogenic scanning transmission electron microscopy (cryo-STEM) to map the spatial distribution of SEI components across the metallic Li anode. We reveal that LiF, an SEI component widely believed to play an important role in battery passivation, is absent within the compact SEI film (∼15 nm); instead, LiF particles (100–400 nm) precipitate across the electrode surface. We term this larger length scale as the indirect SEI regime. On the basis of these observations, we conclude that LiF cannot be a dominant contribution to anode passivation nor does it influence Li+ transport across the compact SEI film. We refine the traditional SEI structure derived from ensemble-averaged characterizations and nuance the role of SEI components on battery performance.
DOI: 10.1021/acscentsci.7b00480
2017
Cited 204 times
Robust Pinhole-free Li<sub>3</sub>N Solid Electrolyte Grown from Molten Lithium
Lithium metal is the ultimate anode choice for high energy density rechargeable lithium batteries. However, it suffers from inferior electrochemical performance and safety issues due to its high reactivity and the growth of lithium dendrites. It has long been desired to develop a materials coating on Li metal, which is pinhole-free, mechanically robust without fracture during Li metal deposition and stripping, and chemically stable against Li metal and liquid electrolytes, all while maintaining adequate ionic conductivity. However, such an ideal material coating has yet to be found. Here we report a novel synthesis method by reacting clean molten lithium foil directly with pure nitrogen gas to generate instantaneously a pinhole-free and ionically conductive α-Li3N film directly bonded onto Li metal foil. The film consists of highly textured large Li3N grains (tens of μm) with (001) crystalline planes parallel to the Li metal surface. The bonding between textured grains is strong, resulting in a mechanically robust film which does not crack even when bent to a 0.8 cm curvature radius and is found to maintain pinhole-free coverage during Li metal deposition and stripping. The measured ionic conductivity is up to 5.2 × 10–4 S cm–1, sufficient for maintaining regular current densities for controllable film thicknesses ranging from 2 to 30 μm. This Li3N coating is chemically stable, isolating the reactive metallic lithium from liquid electrolyte, prevents continuous electrolyte consumption during battery cycling, and promotes dendrite-free uniform lithium plating/stripping underneath. We demonstrated Li|Li4Ti5O12 cells with stable and flat potential profiles for 500 cycles without capacity decay or an increase in potential hysteresis.
DOI: 10.1038/s41467-018-06879-7
2018
Cited 200 times
Flexible and stable high-energy lithium-sulfur full batteries with only 100% oversized lithium
Lightweight and flexible energy storage devices are urgently needed to persistently power wearable devices, and lithium-sulfur batteries are promising technologies due to their low mass densities and high theoretical capacities. Here we report a flexible and high-energy lithium-sulfur full battery device with only 100% oversized lithium, enabled by rationally designed copper-coated and nickel-coated carbon fabrics as excellent hosts for lithium and sulfur, respectively. These metallic carbon fabrics endow mechanical flexibility, reduce local current density of the electrodes, and, more importantly, significantly stabilize the electrode materials to reach remarkable Coulombic efficiency of >99.89% for a lithium anode and >99.82% for a sulfur cathode over 400 half-cell charge-discharge cycles. Consequently, the assembled lithium-sulfur full battery provides high areal capacity (3 mA h cm-2), high cell energy density (288 W h kg-1 and 360 W h L-1), excellent cycling stability (260 cycles), and remarkable bending stability at a small radius of curvature (<1 mm).
DOI: 10.1021/acs.nanolett.9b04815
2020
Cited 184 times
A Fireproof, Lightweight, Polymer–Polymer Solid-State Electrolyte for Safe Lithium Batteries
Safety issues in lithium-ion batteries have raised serious concerns due to their ubiquitous utilization and close contact with the human body. Replacing flammable liquid electrolytes, solid-state electrolytes (SSEs) is thought to address this issue as well as provide unmatched energy densities in Li-based batteries. However, among the most intensively studied SSEs, polymeric solid electrolyte and polymer/ceramic composites are usually flammable, leaving the safety issue unattended. Here, we report the first design of a fireproof, ultralightweight polymer–polymer SSE. The SSE is composed of a porous mechanic enforcer (polyimide, PI), a fire-retardant additive (decabromodiphenyl ethane, DBDPE), and a ionic conductive polymer electrolyte (poly(ethylene oxide)/lithium bis(trifluoromethanesulfonyl)imide). The whole SSE is made from organic materials, with a thin, tunable thickness (10–25 μm), which endorse the energy density comparable to conventional separator/liquid electrolytes. The PI/DBDPE film is thermally stable, nonflammable, and mechanically strong, preventing Li–Li symmetrical cells from short-circuiting after more than 300 h of cycling. LiFePO4/Li half cells with our SSE show a high rate performance (131 mAh g–1 at 1 C) as well as cycling performance (300 cycles at C/2 rate) at 60 °C. Most intriguingly, pouch cells made with our polymer–polymer SSE still functioned well even under flame abuse tests.
DOI: 10.1038/s41560-020-00702-8
2020
Cited 177 times
Ultralight and fire-extinguishing current collectors for high-energy and high-safety lithium-ion batteries
Inactive components and safety hazards are two critical challenges in realizing high-energy lithium-ion batteries. Metal foil current collectors with high density are typically an integrated part of lithium-ion batteries yet deliver no capacity. Meanwhile, high-energy batteries can entail increased fire safety issues. Here we report a composite current collector design that simultaneously minimizes the ‘dead weight’ within the cell and improves fire safety. An ultralight polyimide-based current collector (9 μm thick, specific mass 1.54 mg cm−2) is prepared by sandwiching a polyimide embedded with triphenyl phosphate flame retardant between two superthin Cu layers (~500 nm). Compared to lithium-ion batteries assembled with the thinnest commercial metal foil current collectors (~6 µm), batteries equipped with our composite current collectors can realize a 16–26% improvement in specific energy and rapidly self-extinguish fires under extreme conditions such as short circuits and thermal runaway. Batteries need to be energy-dense as well as safe. Yi Cui and team develop an ultralight polyimide-based current collector with embedded fire retardants that enables lithium-ion batteries with much-enhanced safety and energy density.
DOI: 10.1016/j.joule.2019.01.017
2019
Cited 175 times
Design of Red Phosphorus Nanostructured Electrode for Fast-Charging Lithium-Ion Batteries with High Energy Density
We propose that red phosphorus (P) is an ideal anode material for fast-charging lithium-ion batteries (LIBs) because of the combined advantages of high capacity (6,075 mAh cm−3) and relatively low yet safe lithiation potential (∼0.7 V versus Li/Li+). A red P/C nanocomposite has been fabricated, featuring amorphous red P nanodomains embedded in the nanopores of micrometer-scale porous conductive carbon with interior nanoscale void spaces, a conductive P-free carbon superficial layer, and a high tap density of 1.0 g cm−3. At an industrial-level areal capacity (3 mAh cm−2 or higher), a P/C electrode shows considerably better fast-charging capability than commercial graphite and Li4Ti5O12 electrodes, as well as much higher volumetric capacity and specific capacity based on the whole electrode. Meanwhile, our P/C electrode shows excellent long-term cycling stability with Coulombic efficiency of 100.0% (±0.1%) and 90% capacity retention from the 5th to 500th cycles.
DOI: 10.1038/nnano.2014.117
2014
Cited 173 times
Metamaterial mirrors in optoelectronic devices
DOI: 10.1002/anie.201603897
2016
Cited 167 times
Organotrisulfide: A High Capacity Cathode Material for Rechargeable Lithium Batteries
An organotrisulfide (RSSSR, R is an organic group) has three sulfur atoms which could be involved in multi-electron reduction reactions; therefore it is a promising electrode material for batteries. Herein, we use dimethyl trisulfide (DMTS) as a model compound to study its redox reactions in rechargeable lithium batteries. With the aid of XRD, XPS, and GC-MS analysis, we confirm DMTS could undergo almost a 4 e(-) reduction process in a complete discharge to 1.0 V. The discharge products are primarily LiSCH3 and Li2 S. The lithium cell with DMTS catholyte delivers an initial specific capacity of 720 mAh g(-1) DMTS and retains 82 % of the capacity over 50 cycles at C/10 rate. When the electrolyte/DMTS ratio is 3:1 mL g(-1) , the reversible specific energy for the cell including electrolyte can be 229 Wh kg(-1) . This study shows organotrisulfide is a promising high-capacity cathode material for high-energy rechargeable lithium batteries.
DOI: 10.1021/acs.nanolett.6b04347
2017
Cited 158 times
Shape-Controlled TiO<sub>2</sub> Nanocrystals for Na-Ion Battery Electrodes: The Role of Different Exposed Crystal Facets on the Electrochemical Properties
Rechargeable sodium-ion batteries are becoming a viable alternative to lithium-based technology in energy storage strategies, due to the wide abundance of sodium raw material. In the past decade, this has generated a boom of research interest in such systems. Notwithstanding the large number of research papers concerning sodium-ion battery electrodes, the development of a low-cost, well-performing anode material remains the largest obstacle to overcome. Although the well-known anatase, one of the allotropic forms of natural TiO2, was recently proposed for such applications, the material generally suffers from reduced cyclability and limited power, due to kinetic drawbacks and to its poor charge transport properties. A systematic approach in the morphological tuning of the anatase nanocrystals is needed, to optimize its structural features toward the electrochemical properties and to promote the material interaction with the conductive network and the electrolyte. Aiming to face with these issues, we were able to obtain a fine tuning of the nanoparticle morphology and to expose the most favorable nanocrystal facets to the electrolyte and to the conductive wrapping agent (graphene), thus overcoming the intrinsic limits of anatase transport properties. The result is a TiO2-based composite electrode able to deliver an outstandingly stability over cycles (150 mA h g-1 for more than 600 cycles in the 1.5-0.1 V potential range) never achieved with such a low content of carbonaceous substrate (5%). Moreover, it has been demonstrated for the first time than these outstanding performances are not simply related to the overall surface area of the different morphologies but have to be directly related to the peculiar surface characteristics of the crystals.
DOI: 10.1016/j.joule.2018.05.007
2018
Cited 157 times
An Ultrastrong Double-Layer Nanodiamond Interface for Stable Lithium Metal Anodes
Effective stabilization of lithium metal has been hindered by the exacting requirements for the protection layer. Among all materials, the mechanical strength and electrochemical inertness of diamond is a prime candidate for lithium stabilization. Herein, we successfully rendered this desirable material compatible as lithium metal interface, which strictly satisfied the critical requirements. Our interface possessed the highest modulus among all the lithium coatings (>200 GPa), which can effectively arrest dendrite propagation. Since pinholes are the major failure mechanisms of artificial interfaces, a novel double-layer design was proposed to enhance the defect tolerance, enabling uniform ion flux and mechanical properties as confirmed by both simulation and experiments. Thanks to the multifold advantages of our interface design, high Coulombic efficiency of >99.4% was obtained at 1 mA cm−2; and more than 400 stable cycles were realized in prototypical lithium-sulfur cells with limited lithium, corresponding to an average anode Coulombic efficiency of >99%.
DOI: 10.1021/acsnano.7b03494
2017
Cited 155 times
Revealing the Cell–Material Interface with Nanometer Resolution by Focused Ion Beam/Scanning Electron Microscopy
The interface between cells and nonbiological surfaces regulates cell attachment, chronic tissue responses, and ultimately the success of medical implants or biosensors. Clinical and laboratory studies show that topological features of the surface profoundly influence cellular responses; for example, titanium surfaces with nano- and microtopographical structures enhance osteoblast attachment and host-implant integration as compared to a smooth surface. To understand how cells and tissues respond to different topographical features, it is of critical importance to directly visualize the cell-material interface at the relevant nanometer length scale. Here, we present a method for in situ examination of the cell-to-material interface at any desired location, based on focused ion beam milling and scanning electron microscopy imaging to resolve the cell membrane-to-material interface with 10 nm resolution. By examining how cell membranes interact with topographical features such as nanoscale protrusions or invaginations, we discovered that the cell membrane readily deforms inward and wraps around protruding structures, but hardly deforms outward to contour invaginating structures. This asymmetric membrane response (inward vs outward deformation) causes the cleft width between the cell membrane and the nanostructure surface to vary by more than an order of magnitude. Our results suggest that surface topology is a crucial consideration for the development of medical implants or biosensors whose performances are strongly influenced by the cell-to-material interface. We anticipate that the method can be used to explore the direct interaction of cells/tissue with medical devices such as metal implants in the future.
DOI: 10.1073/pnas.1603810113
2016
Cited 146 times
Metallurgically lithiated SiO <sub>x</sub> anode with high capacity and ambient air compatibility
A common issue plaguing battery anodes is the large consumption of lithium in the initial cycle as a result of the formation of a solid electrolyte interphase followed by gradual loss in subsequent cycles. It presents a need for prelithiation to compensate for the loss. However, anode prelithiation faces the challenge of high chemical reactivity because of the low anode potential. Previous efforts have produced prelithiated Si nanoparticles with dry air stability, which cannot be stabilized under ambient air. Here, we developed a one-pot metallurgical process to synthesize LixSi/Li2O composites by using low-cost SiO or SiO2 as the starting material. The resulting composites consist of homogeneously dispersed LixSi nanodomains embedded in a highly crystalline Li2O matrix, providing the composite excellent stability even in ambient air with 40% relative humidity. The composites are readily mixed with various anode materials to achieve high first cycle Coulombic efficiency (CE) of >100% or serve as an excellent anode material by itself with stable cyclability and consistently high CEs (99.81% at the seventh cycle and ∼99.87% for subsequent cycles). Therefore, LixSi/Li2O composites achieved balanced reactivity and stability, promising a significant boost to lithium ion batteries.
DOI: 10.1021/jacs.7b02622
2017
Cited 139 times
Identifying the Active Surfaces of Electrochemically Tuned LiCoO<sub>2</sub>for Oxygen Evolution Reaction
Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (112̅0) and polar (011̅2) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co4+ sites relative to Co3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (∼0.1 V in overpotential shift at 10 mA cm–2) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. Additionally, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.
DOI: 10.1002/advs.201802353
2019
Cited 138 times
High‐Rate and Large‐Capacity Lithium Metal Anode Enabled by Volume Conformal and Self‐Healable Composite Polymer Electrolyte
The widespread implementation of lithium-metal batteries (LMBs) with Li metal anodes of high energy density has long been prevented due to the safety concern of dendrite-related failure. Here a solid-liquid hybrid electrolyte consisting of composite polymer electrolyte (CPE) soaked with liquid electrolyte is reported. The CPE membrane composes of self-healing polymer and Li+-conducting nanoparticles. The electrodeposited lithium metal in a uniform, smooth, and dense behavior is achieved using a hybrid electrolyte, rather than dendritic and pulverized structure for a conventional separator. The Li foil symmetric cells can deliver remarkable cycling performance at ultrahigh current density up to 20 mA cm-2 with an extremely low voltage hysteresis over 1500 cycles. A large areal capacity of 10 mAh cm-2 at 10 mA cm-2 could also be obtained. Furthermore, the Li|Li4Ti5O12 cells based on the hybrid electrolyte achieve a higher specific capacity and longer cycling life than those using conventional separators. The superior performances are mainly attributed to strong adhesion, volume conformity, and self-healing functionality of CPE, providing a novel approach and a significant step toward cost-effective and large-scalable LMBs.
DOI: 10.1021/acsnano.8b01619
2018
Cited 134 times
Malic Acid Carbon Dots: From Super-resolution Live-Cell Imaging to Highly Efficient Separation
As-synthesized malic acid carbon dots are found to possess photoblinking properties that are outstanding and superior compared to those of conventional dyes.Considering their excellent biocompatibility, malic acid carbon dots are suitable for super-resolution fluorescence localization microscopy under a variety of conditions, as we demonstrate in fixed and live trout gill epithelial cells.In addition, during imaging experiments, the so-called "excitation wavelength-dependent" emission was not observed for individual as-made malic acid carbon dots, which motivated us to develop a time-saving and highthroughput separation technique to isolate malic acid carbon dots into fractions of different particle size distributions using C 18 reversed-phase silica gel column chromatography.This post-treatment allowed us to determine how particle size distribution influences the optical properties of malic acid carbon dot fractions, that is, optical band gap energies and photoluminescence behaviors.
DOI: 10.1002/cey2.9
2019
Cited 118 times
Nanodiamonds for energy
Abstract Carbon materials have been playing important roles in advancing energy‐related technologies and offering great promise to addressing the rising global energy demands and environmental issues. Nanodiamonds, an exciting class of carbon materials, with excellent mechanical, chemical, electronic, and optical properties, have great potentials in energy‐related applications. In this contribution, we summarized some of the recent progress on nanodiamonds for energy storage, conversion, and other related applications in sustainable energy research. We discussed the promising opportunities and outlooks for nanodiamonds in energy‐related fields.
DOI: 10.1038/s41467-021-26384-8
2021
Cited 99 times
Integrated cooling (i-Cool) textile of heat conduction and sweat transportation for personal perspiration management
Abstract Perspiration evaporation plays an indispensable role in human body heat dissipation. However, conventional textiles tend to focus on sweat removal and pay little attention to the basic thermoregulation function of sweat, showing limited evaporation ability and cooling efficiency in moderate/profuse perspiration scenarios. Here, we propose an integrated cooling (i-Cool) textile with unique functional structure design for personal perspiration management. By integrating heat conductive pathways and water transport channels decently, i-Cool exhibits enhanced evaporation ability and high sweat evaporative cooling efficiency, not merely liquid sweat wicking function. In the steady-state evaporation test, compared to cotton, up to over 100% reduction in water mass gain ratio, and 3 times higher skin power density increment for every unit of sweat evaporation are demonstrated. Besides, i-Cool shows about 3 °C cooling effect with greatly reduced sweat consumption than cotton in the artificial sweating skin test. The practical application feasibility of i-Cool design principles is well validated based on commercial fabrics. Owing to its exceptional personal perspiration management performance, we expect the i-Cool concept can provide promising design guidelines for next-generation perspiration management textiles.
DOI: 10.1021/jacs.1c03868
2021
Cited 86 times
Potentiometric Measurement to Probe Solvation Energy and Its Correlation to Lithium Battery Cyclability
The electrolyte plays a critical role in lithium-ion batteries, as it impacts almost every facet of a battery’s performance. However, our understanding of the electrolyte, especially solvation of Li+, lags behind its significance. In this work, we introduce a potentiometric technique to probe the relative solvation energy of Li+ in battery electrolytes. By measuring open circuit potential in a cell with symmetric electrodes and asymmetric electrolytes, we quantitatively characterize the effects of concentration, anions, and solvents on solvation energy across varied electrolytes. Using the technique, we establish a correlation between cell potential (Ecell) and cyclability of high-performance electrolytes for lithium metal anodes, where we find that solvents with more negative cell potentials and positive solvation energies—those weakly binding to Li+—lead to improved cycling stability. Cryogenic electron microscopy reveals that weaker solvation leads to an anion-derived solid-electrolyte interphase that stabilizes cycling. Using the potentiometric measurement for characterizing electrolytes, we establish a correlation that can guide the engineering of effective electrolytes for the lithium metal anode.
DOI: 10.1038/s41893-021-00836-x
2021
Cited 84 times
Coloured low-emissivity films for building envelopes for year-round energy savings
DOI: 10.1039/d0sc05743f
2021
Cited 83 times
Multicolor polymeric carbon dots: synthesis, separation and polyamide-supported molecular fluorescence
Multicolor carbon dots (CDs) have been developed recently and demonstrate great potential in bio-imaging, sensing, and LEDs. However, the fluorescence mechanism of their tunable colors is still under debate, and efficient separation methods are still challenging. Herein, we synthesized multicolor polymeric CDs through solvothermal treatment of citric acid and urea in formamide. Automated reversed-phase column separation was used to achieve fractions with distinct colors, including blue, cyan, green, yellow, orange and red. This work explores the physicochemical properties and fluorescence origins of the red, green, and blue fractions in depth with combined experimental and computational methods. Three dominant fluorescence mechanism hypotheses were evaluated by comparing time-dependent density functional theory and molecular dynamics calculation results to measured characteristics. We find that blue fluorescence likely comes from embedded small molecules trapped in carbonaceous cages, while pyrene analogs are the most likely origin for emission at other wavelengths, especially in the red. Also important, upon interaction with live cells, different CD color fractions are trafficked to different sub-cellular locations. Super-resolution imaging shows that the blue CDs were found in a variety of organelles, such as mitochondria and lysosomes, while the red CDs were primarily localized in lysosomes. These findings significantly advance our understanding of the photoluminescence mechanism of multicolor CDs and help to guide future design and applications of these promising nanomaterials.
DOI: 10.1038/s41586-022-05249-0
2022
Cited 44 times
Single-cell genomic variation induced by mutational processes in cancer
Abstract How cell-to-cell copy number alterations that underpin genomic instability 1 in human cancers drive genomic and phenotypic variation, and consequently the evolution of cancer 2 , remains understudied. Here, by applying scaled single-cell whole-genome sequencing 3 to wild-type, TP53- deficient and TP53 -deficient; BRCA1 -deficient or TP53 -deficient; BRCA2- deficient mammary epithelial cells (13,818 genomes), and to primary triple-negative breast cancer (TNBC) and high-grade serous ovarian cancer (HGSC) cells (22,057 genomes), we identify three distinct ‘foreground’ mutational patterns that are defined by cell-to-cell structural variation. Cell- and clone-specific high-level amplifications, parallel haplotype-specific copy number alterations and copy number segment length variation (serrate structural variations) had measurable phenotypic and evolutionary consequences. In TNBC and HGSC, clone-specific high-level amplifications in known oncogenes were highly prevalent in tumours bearing fold-back inversions, relative to tumours with homologous recombination deficiency, and were associated with increased clone-to-clone phenotypic variation. Parallel haplotype-specific alterations were also commonly observed, leading to phylogenetic evolutionary diversity and clone-specific mono-allelic expression. Serrate variants were increased in tumours with fold-back inversions and were highly correlated with increased genomic diversity of cellular populations. Together, our findings show that cell-to-cell structural variation contributes to the origins of phenotypic and evolutionary diversity in TNBC and HGSC, and provide insight into the genomic and mutational states of individual cancer cells.
DOI: 10.1002/adfm.202211955
2023
Cited 20 times
Tailoring Multifunctional Self‐Assembled Hole Transporting Molecules for Highly Efficient and Stable Inverted Perovskite Solar Cells
Abstract The self‐assembled hole transporting molecules (SAHTMs) bearing anchoring groups have been established as the hole transporting layers (HTLs) for highly efficient p–i–n perovskite solar cells (PSCs), yet their stability and engineering at the molecular level remain challenging. A topological design of highly anisotropic aligned SAHTM‐based HTLs for operationally stable PSCs that exhibit exceptional solar‐to‐electric power conversion efficiencies (PCEs) is demonstrated. The judiciously designed multifunctional self‐assembled molecules comprise the donor–acceptor subunit for hole transporting and the phosphonic acid group for anchoring, realizing face‐on π‐stacking parallel to the transparent conductive oxide substrate. The high affinity of SAHTMs to the multi‐crystalline perovskite thin film benefits passivating the perovskite buried interface, strengthening interfacial contact while facilitating interfacial hole transfer. Consequently, highly efficient p–i–n PSC devices are obtained with a champion PCE of 23.24% and outstanding operational stability toward various environmental factors including long‐term full sunlight soaking at evaluated temperatures. Perovskite solar modules with a champion efficiency approaching 20% are also fabricated for an active device area above 17 cm 2 .
DOI: 10.1063/1.3425767
2010
Cited 184 times
Printed energy storage devices by integration of electrodes and separators into single sheets of paper
We report carbon nanotube thin film-based supercapacitors fabricated with printing methods, where electrodes and separators are integrated into single sheets of commercial paper. Carbon nanotube films are easily printed with Meyer rod coating or ink-jet printing onto a paper substrate due to the excellent ink absorption of paper. A specific capacity of 33 F/g at a high specific power of 250 000 W/kg is achieved with an organic electrolyte. Such a lightweight paper-based supercapacitor could be used to power paper electronics such as transistors or displays.
DOI: 10.1002/(sici)1097-4628(19981219)70:12<2371::aid-app9>3.0.co;2-4
1998
Cited 183 times
Isothermal and nonisothermal crystallization kinetics of nylon-11
Journal of Applied Polymer ScienceVolume 70, Issue 12 p. 2371-2380 Full Access Isothermal and nonisothermal crystallization kinetics of nylon-11 Siyang Liu, Siyang Liu Polymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, ChinaSearch for more papers by this authorYingning Yu, Yingning Yu Polymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, ChinaSearch for more papers by this authorYi Cui, Yi Cui Polymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, ChinaSearch for more papers by this authorHongfang Zhang, Hongfang Zhang Polymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, ChinaSearch for more papers by this authorZhishen Mo, Corresponding Author Zhishen Mo Polymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, ChinaPolymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China===Search for more papers by this author Siyang Liu, Siyang Liu Polymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, ChinaSearch for more papers by this authorYingning Yu, Yingning Yu Polymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, ChinaSearch for more papers by this authorYi Cui, Yi Cui Polymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, ChinaSearch for more papers by this authorHongfang Zhang, Hongfang Zhang Polymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, ChinaSearch for more papers by this authorZhishen Mo, Corresponding Author Zhishen Mo Polymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, ChinaPolymer Physics Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China===Search for more papers by this author First published: 12 December 1998 https://doi.org/10.1002/(SICI)1097-4628(19981219)70:12<2371::AID-APP9>3.0.CO;2-4Citations: 173AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract Analysis of the isothermal, and nonisothermal crystallization kinetics of Nylon-11 is carried out using differential scanning calorimetry. The Avrami equation and that modified by Jeziorny can describe the primary stage of isothermal and nonisothermal crystallization of Nylon-11. In the isothermal crystallization process, the mechanism of spherulitic nucleation and growth are discussed; the lateral and folding surface free energies determined from the Lauritzen–Hoffman equation are ς = 10.68 erg/cm2 and ςe = 110.62 erg/cm2; and the work of chain folding q = 7.61 Kcal/mol. In the nonisothermal crystallization process, Ozawa analysis failed to describe the crystallization behavior of Nylon-11. Combining the Avrami and Ozawa equations, we obtain a new and convenient method to analyze the nonisothermal crystallization kinetics of Nylon-11; in the meantime, the activation energies are determined to be −394.56 and 328.37 KJ/mol in isothermal and nonisothermal crystallization process from the Arrhonius form and the Kissinger method. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2371–2380, 1998 Citing Literature Volume70, Issue1219 December 1998Pages 2371-2380 RelatedInformation
DOI: 10.1021/nl101944e
2010
Cited 174 times
High Speed Water Sterilization Using One-Dimensional Nanostructures
The removal of bacteria and other organisms from water is an extremely important process, not only for drinking and sanitation but also industrially as biofouling is a commonplace and serious problem. We here present a textile based multiscale device for the high speed electrical sterilization of water using silver nanowires, carbon nanotubes, and cotton. This approach, which combines several materials spanning three very different length scales with simple dying based fabrication, makes a gravity fed device operating at 100000 L/(h m2) which can inactivate >98% of bacteria with only several seconds of total incubation time. This excellent performance is enabled by the use of an electrical mechanism rather than size exclusion, while the very high surface area of the device coupled with large electric field concentrations near the silver nanowire tips allows for effective bacterial inactivation.
DOI: 10.1021/nl101884h
2010
Cited 173 times
Ultrathin Topological Insulator Bi<sub>2</sub>Se<sub>3</sub> Nanoribbons Exfoliated by Atomic Force Microscopy
Ultra-thin topological insulator nanostructures, in which coupling between top and bottom surface states takes place, are of great intellectual and practical importance.Due to the weak Van der Waals interaction between adjacent quintuple layers (QLs), the layered bismuth selenide (Bi 2 Se 3 ), a single Dirac-cone topological insulator with a large bulk gap, can be exfoliated down to a few QLs.In this paper, we report the first controlled mechanical exfoliation of Bi 2 Se 3 nanoribbons (> 50 QLs) by an atomic force microscope (AFM) tip down to a single QL.Microwave impedance microscopy is employed to map out the local conductivity of such ultra-thin nanoribbons, showing drastic difference in sheet resistance between 1~2 QLs and 4~5 QLs.Transport measurement carried out on an exfoliated (≤5 QLs) Bi 2 Se 3 device shows nonmetallic temperature dependence of resistance, in sharp contrast to the metallic behavior seen in thick (>50 QLs) ribbons.These AFM-exfoliated thin nanoribbons afford interesting candidates for studying the transition from quantum spin Hall surface to edge states.
DOI: 10.1039/c0cc02078h
2011
Cited 171 times
Si nanoparticle-decorated Si nanowire networks for Li-ion battery anodes
We designed and fabricated binder-free, 3D porous silicon nanostructures for Li-ion battery anodes, where Si nanoparticles electrically contact current collectors via vertically grown silicon nanowires. When compared with a Si nanowire anode, the areal capacity was increased by a factor of 4 without having to use long, high temperature steps under vacuum that vapour–liquid–solid Si nanowire growth entails.
DOI: 10.1021/nn301339g
2012
Cited 161 times
<i>In Situ</i> X-ray Diffraction Studies of (De)lithiation Mechanism in Silicon Nanowire Anodes
Silicon is a promising anode material for Li-ion batteries due to its high theoretical specific capacity. From previous work, silicon nanowires (SiNWs) are known to undergo amorphorization during lithiation, and no crystalline Li–Si product has been observed. In this work, we use an X-ray transparent battery cell to perform in situ synchrotron X-ray diffraction on SiNWs in real time during electrochemical cycling. At deep lithiation voltages the known metastable Li15Si4 phase forms, and we show that avoiding the formation of this phase, by modifying the SiNW growth temperature, improves the cycling performance of SiNW anodes. Our results provide insight on the (de)lithiation mechanism and a correlation between phase evolution and electrochemical performance for SiNW anodes.