Low-Temperature Treated Lignin as Both Binder and Conductive

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Low-temperature Treated Lignin as Both Binder and Conductive Additive for Silicon Nanoparticle Composite Electrodes in Lithium-Ion Batteries Tao Chen, Qinglin Zhang, Jie Pan, Jiagang Xu, Yiyang Liu, Mohanad Al-Shroofy, and Yang-Tse Cheng ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b11500 • Publication Date (Web): 09 Nov 2016 Downloaded from http://pubs.acs.org on November 13, 2016

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ACS Applied Materials & Interfaces

Low-temperature Treated Lignin as Both Binder and Conductive Additive for Silicon Nanoparticle Composite Electrodes in Lithium-Ion Batteries Tao Chen,*1 Qinglin Zhang, †1 Jie Pan, ‡1 Jiagang Xu,1 Yiyang Liu,2 Mohanad Al-Shroofy,1 and Yang-Tse Cheng1 1

Department of Chemical and Materials Engineering, University of Kentucky, KY, USA 40506-

0046. 2

Department of Chemistry, University of Kentucky, KY, USA 40506-0055.

KEYWORDS: Lithium ion battery, anode material, binder-free anode, bio-renewable, siliconcarbon composite, lignin

ABSTRACT

This work demonstrates a high performance and durable silicon nanoparticle based negative electrode in which conventional polymer binder and carbon black additive are replaced with lignin. The mixture of silicon nanoparticles and lignin, a low cost, renewable, and widely available biopolymer, was coated on copper substrate using the conventional slurry mixing and

ACS Paragon Plus Environment

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coating method and subsequently heat treated to form the composite electrode. The composite electrode showed excellent electrochemical performance with an initial discharge capacity of up to 3086 mAh g-1 and retaining 2378 mAh g-1 after 100 cycles at 1A g-1. Even at relatively high areal loading of ~1 mg cm-2, an areal capacity of ~2 mAh cm-2 was achieved. The composite electrode also displayed excellent rate capability and performance in a full-cell setup. Through synergistic analysis of X-ray photoelectron spectroscopy (XPS), Raman, and nano-indentation experiment results, we attribute the amazing properties of Si/lignin electrodes to the judicious choice of heat treatment temperature at 600°C. At this temperature lignin undergoes complex compositional change during which a balance between development of conductivity and retaining of polymer flexibility is realized. We hope this work could lead to practicable silicon based negative electrodes and stimulate the interest in the utilization of bio-renewable resources in advanced energy applications.

1. Introduction The demand for higher energy density and low cost lithium ion batteries is ever increasing as market and policies promote the proliferation of electric vehicles.1-2 Currently, graphite is the mainstay negative electrode material for commercial lithium ion batteries, delivering a theoretical specific capacity of 372 mAh g-1. Alternative materials such as pure lithium metal electrode and graphene are being developed,3-4 although they all face serious challenges. Silicon is one of the promising negative electrode materials with the theoretical capacity of 4200 mAh g-1, more than 10 times higher than that of graphite.5 While silicon negative electrodes boast the advantages of high theoretical capacity, low lithiation/delithiation


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potential, and natural abundance, bulk silicon suffers from large volume change (300%) and pulverization leading to its ultimate failure well short of a few hundred cycles that is considered bare minimum for replacing graphite.6-7 A number of strategies have been studied to accommodate silicon volume expansion, including the development of binders,8-9 dispersion of silicon in inactive/active composites,9-13 and devising of novel nanostructures.14-17 Among these approaches, silicon-carbon (Si-C) based composites are especially promising because carbon is comparatively flexible, electronically conductive, and easy to obtain.18-19 Silicon and carbon materials have been composited through a number of methods, e.g., electrospinning, ball-milling, coating, and chemical self-assemblies.12,

18, 20-23

Although these methods have improved the

performance of silicon negative electrodes considerably, they

introduced, in some cases,

complicated synthesis steps which made the composites uneconomical or inactive components which reduced energy density of the composite electrodes. We believe simple synthesis steps that utilized renewable materials without inactive components are important for developing practical silicon based electrodes. Low cost and renewable lignin, which constitutes up to 30% dry mass of the organic carbon on earth, is widely available from paper and pulp mills which produced in excess of 50 million tons annually.24 Generally burnt for energy on site, lignin is gradually finding its way into high value-added products.25 For example, Kadla et al. used lignin as the precursor for making carbon fibers.26 Tenhaeff et al. fabricated lignin into robust lignin fiber mats for lithium ion battery negative electrodes.27 Recently, lignin has also been composited with pitch as the precursor for efficient sodium ion batteries.28 Aside from being a by-product of paper and pulp industry, lignocellulosic mass for the renewable fuel industry is forecasted to reach the annual production of 60 million tons by 2020 as mandated by the US Environmental Protection Agency (EPA).29 With such a


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high abundancy, it is critical and profitable to find high value-added products for lignin to improve the renewable bio-resource landscape. We propose lignin as a very competitive additive for making high performance silicon based lithium ion battery negative electrodes. Previously, we showed that a heat treatment process at 800oC would convert a siliconlignin slurry to a binder-free Si-C composite electrode with high and stable electrochemical performance in which the lignin acted as both the conductive agent and binder.30 However, the high temperature treatment resulted in suboptimal utilization of silicon possibly due to the rigid structure of the lignin-derived carbonaceous network. To further improve the cyclability and utilization of silicon nanoparticles, we explore in this report, a low-temperature heat treatment of the silicon-lignin composite, similar to a low-temperature treatment of Si-cyclized polyacrylonitrile (PAN) approach by Piper et al.31 They showed that by limiting the pyrolysis temperature to 300-500°C, the cyclization of PAN proceeds without carbonization, thus maintaining polymeric properties while still introducing delocalized sp2 π bonding for electronic conductivity. On lignin molecules there exist an abundance of various chemical moieties such as methoxyls, phenols, and hydroxyls while lignin itself is a cross-linked biopolymer with binderlike properties and usages.32 We speculated that, at intermediate heat treatment temperatures of 400-600°C, lignin could be sufficiently carbonized providing excellent electronic conductivity via localized sp2 π while maintaining some of its polymeric flexibility, allowing the composite to fully utilize silicon capacity and accommodate volume expansion. To test our hypothesis, we used scanning electron microscopy (SEM) to show that the Si-Lig composite was very robust and stable after a high number of cycles. Transmission electron microscopy (TEM) showed that silicon nanoparticles were uniformly dispersed and coated by a thin layer of amorphous carbon acting as a protection layer. Synergistic results of Raman, XPS, and mechanical property


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measurements by nano-indentation helped explain the chemical composition evolution of lignin during the heat treatment and proved that the Si-Lig composite was sufficiently electronically conductive while being flexible compared to higher temperature treated counterparts. Together these attributes ensured a Si-Lig composite with excellent electrochemical performance.

2. Experimental Section 2.1 Preparation of Si-Lig composite Kraft lignin (Indulin AT), supplied by Mead Westvaco as a brown powder, is a purified form of Kraft pine lignin. It is derived by further acid hydrolysis of Kraft lignin, which removes both the sodium and the hemicellulose. The lignin was first mixed with 0.5 wt% polyethylene oxide (PEO, 1x106 MW, Sigma Aldrich) by spatula, then the powder mixture was dissolved in dimethylformamide (DMF, Sigma Aldrich) with a weight ratio of 15%. The solution was heated to 60°C under constant magnetic stirring for 2 hours. Afterwards, silicon nanoparticles of diameters 30-50 nm (Nanostructured & Amorphous Materials) were added to the solution with a weight ratio of 15% to DMF. The solution was magnetically stirred for 6 hours at 60°C while going through sonication for 5 mins every 2 hours. A Mazerustar KK-250S planetary mixer was also used every 2 hours to ensure adequate mixing. The solution was stirred and heated until reaching a suitable viscosity for slurry coating onto copper foil by a doctor blade with a gap spacing of 127 µm. After drying in air, the coated copper foil was dried under vacuum at 120°C overnight to obtain a uniform Si-Lig film. The average thickness of the composite film is ~25 µm.


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The dried silicon-lignin on copper foil was heat treated in a tube furnace with argon atmosphere at a step rate of 2 °C /min up to 400-600°C, then held for 10 min. For making electrodes, 12 mm disks were cut and stored to be assembled into coin cells.

2.2 Coin cell fabrication and electrochemical testing For electrochemical performance of silicon-lignin half-cell electrode, coin cells (CR2025 type) were assembled in an argon filled glove box, using Li foil as the counter/reference electrode, Celgard 2400 membrane as the separator, and 1M LiPF6 in ethylene carbonate and diethyl carbonate (EC: DEC=1:1 vol%, BASF) with 10wt% fluoroethylene carbonate (FEC, BASF) additive as the electrolyte. A total of more than 20 coin cells made from 3 batches were tested in half cell setups. For full cell NMC (LiNi1/3Mn1/3Co1/3O2， Umicore) electrode replaced the Li metal foil as the cathode electrode. The NMC electrode was prepared using the conventional slurry coating method with a composition of 92 wt% NMC/4 wt% carbon black (Super P C65, TIMCAL/4 wt% polyvinylidene fluoride (PVDF, No. 1100, Kureha, Japan). The average loading and density of the NMC electrode were ~14 mg cm-2 and ~1.7 g cm-3, respectively and the loading and density of the silicon-lignin electrode were ~1mg cm-2 and ~0.4 g cm-3, respectively. Masses of the negative silicon-lignin electrode and positive NMC electrode were balanced so that the total capacity N/P ratio of the electrodes was ~1:1. The electrodes were assembled into CR2025 type full cell configuration coin cells and 6 full cells were tested. Electrochemical tests were performed using a Bio-Logic potentiostat (VMP-3) at room temperature. The electrochemical properties of the electrodes were measured within a voltage range of 0.015-1.2 V using constant current mode. Impedance was measured potentiostatically


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by applying an AC voltage of 10mV amplitude in the range of 100 kHz to 100 mHz directly using coin cells after a specific number of cycles. The Si wt% content of the composite was calculated by punching out individual electrodes (12 mm diameter) and weighing the mass loss after heat treatment, where the lignin component lost mass and silicon mass remained constant. The specific capacities of the electrodes were normalized based on the weight of Si in the composite or the total weight of the composite. The mass loading of the silicon-lignin composite electrodes was 0.9 to1.1mg cm-2, and the Si loading 0.60 to 0.73 mg cm-2.

2.3 Characterizations Scanning electron microscopy (SEM) images were recorded using a Hitachi S-4300 microscope with a 6 kV voltage in the imaging mode. The structure of the silicon-lignin composite electrodes was examined with a JEOL 2010F transmission electron microscope (TEM). X-ray photoelectron spectroscopy was performed on a Thermo Scientific K-Alpha system with Al Kα radiation. Nano-indentation was performed on an Agilent Technologies Nano Indenter G200. The maximum load was 9.8mN, the loading rate was 0.49mN/s, and the hold time at maximum load was 10 s. Depth profile (Continuous Stiffness Measurement mode) was studied between 0-3000 nm and average results were obtained for depth either 200-800 nm or 1000-3000 nm where the elastic modulus and hardness were consistent according to Oliver and Pharr.33-34 Raman analysis was performed on a Thermo Scientific DXR Raman microscope. Peak analysis was done using OriginPro.

3. Results and discussions


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The electrochemical performance of silicon-lignin half cells are presented in Figure 1. The electronic conductivity of silicon-lignin composite is likely very low after heat treatment at 400°C leading to almost no capacity. The main transition for the development of electronic conductivity for lignin in our case appeared to be between 400°C and 500°C. Figure 1a shows the initial charge (lithiation) and discharge (delithiation) capacity for silicon-lignin composite treated at 500oC to be ~3000 mAh g-1 and 2330 mAh g-1. Through cycles 2 to 5 capacity gradually increased until the coulombic efficiency (CE) was close to 100%. Figure 1b shows that the initial charge (lithiation) and discharge (delithiation) capacity for silicon-lignin composite treated at 600°C is ~3780 mAh g-1 and 3086 mAh g-1 respectively calculated to the weight of silicon, which corresponds to 2500 mAh g-1 and 2050 mAh g-1 normalized to the weight of the entire composite electrode. Both electrodes showed a characteristic long plateau during the first lithiation at 0.99. The ratios of ID/IG were calculated using the fitted peaks and found to be 2.19 for 400oC, 1.90 for 500oC, and 1.84 for 600oC samples. Our findings are consistent with the literature that ID/IG decreases with increasing heat treatment temperature, implying a higher degree of ordering for carbons.44 From the characterization results, it is evident that heat treatment at 400-600oC caused graphitization of lignin, bringing forth electronic conductivity.


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Figure 3. (a) C 1s XPS spectra of silicon-lignin composite treated at various temperatures (b) Raman spectra of silicon-lignin composite treated at various temperatures shown with the typical D and G bands.

We believe that performance of a binder should be dependent on its mechanical properties, in particular elastic modulus and hardness. In the case of silicon nanoparticles, however, there seems to be few studies establishing a correlation between these mechanical properties and the electrochemical performance of a binder. Some previous research has indicated that mechanical properties of binders are one of the key factors in determining their performance.45-46 Therefore, we have carried out detailed nano-indentation measurements to


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obtain, in Table 1, the mechanical properties of silicon-lignin composites heat treated at two different temperatures. We found that the modulus of heat treated lignin composited with silicon nanoparticles was much lower than carbon fibers using lignin as a precursor due to difference in configuration and heat treatment protocol. The elastic modulus of lignin without heat treatment is in the range of ~3 GPa and carbon fibers spun from lignin precursor had modulus in the range of 39 to 61 GPa.47-48 A notable increase in elastic modulus and hardness is seen for silicon-lignin composites treated at 600oC compared to 800oC, which shows a much stiffer composite was formed due to carbons being more ordered at higher temperatures such as forming graphite-like domains. While this brought an increase in conductivity, it likely decreased polymer-like properties of the composite resulting in lower silicon utilization and volume accommodation ability. These difference in mechanical properties helped explain why silicon-lignin composite treated at temperatures of 600oC had much improved electrochemical performance over our previous publication where it was treated at 800oC.30

E (GPa)

H (GPa)

Mean

S.D.

Mean

S.D.

Silicon-lignin composite (600oC)

6.23

0.72

0.19

0.04

Silicon-lignin composite (800oC)

16.64

3.73

0.82

0.34


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Table 1. Summary of elastic modulus (E) and hardness (H) for silicon-lignin composites.

To investigate the electronic conductivity we studied silicon-lignin composite heat treated at 400, 500, and 600oC by electrochemical impedance spectroscopy (EIS). EIS measurements for half-cells were conducted during the cycling process and shown in Figure 4a. The EIS plots usually consist of a semicircle at high frequency which represents the resistance of the electrolyte and charge-transfer, and a Warburg tail at lower frequencies due to diffusion-resistance from the electrode material. For the 500°C electrode the resistance at high frequencies increased over the course of cycling. For the 600°C cell the resistance at high frequencies did not dramatically change, but the resistance at lower frequencies increased over the course of cycling. An equivalent circuit shown in Figure 4b was used to fit experimental data over the high and medium frequency range, and the fitted curves were plotted with the experimental data in closeup in Figure S6.49 Overall the impedance values were low for such a silicon-based composite electrode.50


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Figure 4. (a) Nyquist plots for the Si-Lig composites heat treated at 500°C and 600°C after 20 and 100 cycles. (b) Equivalent circuit used for fitting for the experimental data.

Based on the characterization results, we suggests the structure of silicon-lignin composite electrode as illustrated in Figure 5. Prior to heat treatment, Si nanoparticles are uniformly dispersed and coated with the heavily cross-linked lignin while lignin also forms a 3D matrix surrounding the Si nanoparticles. The pyrolysis of lignin is a complex process where


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various volatile compounds and a solid residue are obtained after heat treatment.18, 51 The major gaseous products are methanol, formaldehyde, acetic acid, light hydrocarbons, in addition to CO, CO2, and H2O. The solid residue is polycyclic aromatic hydrocarbon at intermediate temperatures from 150-550oC and increasingly devoid of hydrogen and oxygen at higher temperatures. The pyrolysis of lignin is also accompanied by mass loss, and the typical char yield is 40~50% at 600°C, depending on the heating protocol and lignin type.26 For silicon-lignin composites upon heat treatment in inert gas atmosphere, lignin is expected to carbonize leaving behind a porous carbon network with graphitic domains high electronic conductivity and nongraphitic domains of high flexibility surrounding Si nanoparticles. It is also important to note that the addition of 0.5 wt% of PEO helped to stabilize lignin coating on silicon nanoparticles during the heating up process presumably due to (1) promotion of hydrogen bonding between lignin blends, thus increasing the viscosity of Si-lignin composite52 (2) Enhanced silicon nanoparticle-lignin hydrogen bonding interactions, allowing for better encapsulation of silicon nanoparticles. 53 PEO is regularly added to lignin blends to ensure better electrospinning or lower the lignin critical concentration required for spinning.54-55


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Figure 5. Schematic illustration of the silicon-lignin composite after heat treatment.

4. Conclusions We demonstrated that renewable, low-cost, and widely available biopolymer lignin could be composited with silicon nanoparticles under the appropriate low temperature heat treatment to yield composite negative electrodes with exceptional electrochemical performance, retaining 2378 mAh g-1 after 100 cycles at 1A g-1. We explored and presented possible chemical composition changes of lignin during the heat treatment. We elucidated the effects of heat treatment on lignin as a binder and conductive agent. The performance of this binder-free and conductive additive free electrode is comparable to electrodes where conventional binders or polymer binders were used.9, 39, 50, 56-57 Although lignin has been previously explored for use in


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sodium ion batteries and carbon fibers as active material/support for lithium ion batteries,28, 58-59, this work demonstrates it effectiveness in silicon-based negative electrodes. This simple system also presents many opportunities for future studies. Although halfcell performance was remarkable, full-cell performance of the composite electrode shows that there are many challenges to be solved in practical silicon-based electrodes in limiting the loss of lithium, especially with high Si loadings. Based on the results and previous literature we believe that artificial surface SEI coatings of a combination of Al2O3/LiF or pre-lithiation to compensate the lithium loss may be two of the approaches to further improve the electrode performance.60-61 .

ASSOCIATED CONTENT Supporting Information. Full cell electrochemical performance of silicon-lignin composite, SEM and TEM images of post-cycling silicon-lignin composite, EDX mapping, fitted Nyquist plot, and table with deconvoluted C 1s XPS peak areas and ratios are available in the supporting information.


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AUTHOR INFORMATION Corresponding Author *Email: [email protected] Current Address †

Optimal CAE, 47802 West Anchor Court, Plymouth, MI, 48170

‡

National Renewable Energy Laboratory, Golden, Colorado, 80401

Funding Sources National Science Foundation Grant No. 1355438 (Powering the Kentucky Bio-economy for a Sustainable Future). Notes The authors declare no competing financial interests. ACKNOWLEDGMENT We would like to thank Long Zhang for XPS measurements, Yikai Wang for nano-indentation experiments, Dali Qian for the helps with SEM and TEM, and Laura Grueneberg for discussions. We are grateful for the financial support from National Science Foundation Grant No. 1355438 (Powering the Kentucky Bio-economy for a Sustainable Future). REFERENCES

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Low-Temperature Treated Lignin as Both Binder and Conductive

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