Dendrite-Free Composite Li Anode Assisted by Ag Nanoparticles in a

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A dendrite-free composite Li anode assisted by Ag nanoparticles in wood-derived carbon frame Huiyu Song, Xilong Chen, Guangli Zheng, Xijuan Yu, Shangfeng Jiang, Zhiming Cui, Li Du, and Shijun Liao ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 30 Apr 2019 Downloaded from http://pubs.acs.org on April 30, 2019

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ACS Applied Materials & Interfaces

A dendrite-free composite Li anode assisted by Ag nanoparticles in wood-derived carbon frame Huiyu Song†,#, Xilong Chen†,#, Guangli Zheng†, Xijuan Yu‡, Shangfeng Jiang§, Zhiming Cui†, Li Du†*, Shijun Liao†

†

The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, China

‡ Key

Laboratory of Opticelectric Sensing and Analytical Chemistry for Life Science, MOE, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

§

Zhengzhou Yutong Bus Co.Ltd., Yutong Industrial Park, Yutong Road, Zhengzhou, 450000, China

# Huiyu

Song and Xilong Chen contributed equally to this work.

*Email:

[email protected]

KEYWORDS: Wood-derived carbon; Ag nanoseeds; Lithiophilicity; Dendrites; Lithium anode.

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ABSTRACT: Using lithium metal as anode in lithium batteries has attracted great attentions due to its ultrahigh theoretical capacity of 3,860 mA h g-1. However, the uneven deposition of lithium will cause dendrites, resulting in poor cycling performance. Herein, a dendrite-free Li composite anode is developed by anchoring Ag nanoparticles in wood-derived carbon frame. The composite anode is integrally-formed and has enough room for Li deposition due to the aligned open channels preserved from natural wood, which can decrease anode volume change greatly during cycling. The Ag nanoparticles, serving as seeds of lithium deposition, can help the even deposition of lithium in the channels of carbon matrix due to its lithiophilicity and then avoid lithium dendrites formation. The composite anode exhibits excellent cyclic performance over 450 hours at 1 mA cm-2 and over 300 hours at 3 mA cm-2. The full cell of AgWDC@LFP also exhibits a smallest electrochemical polarization from 0.2 C to 5 C, and a stable specific capacity and a high Coulombic efficiency at 1 C after a long time cycle. These results indicate that Ag nanoparticles play an important role to restrain dendrites formation during lithium plating/stripping. The wood-derived composite cathode can achieve no lithium dendrites and can be applied in other storage batteries.

INTRODUCTION With the increasing demands of portable smart devices and electric vehicles, it is an emergency task to develop better energy storage technologies to meet the needs of commercial applications.1-5 Lithium as anode is the most promising choice due to their extremely high theoretical capacity (3860 mA h g-1), low standard potential (-3.04 V vs. standard hydrogen electrode) and the lightest metal weight (0.53 g cm-3).6 However, there exist lots of intricate troubles which need to be solved before the practical application of lithium batteries.7, 8 To put simply, lithium plating/stripping process is uncontrollable and prone to form lithium dendrite which could make short circuit of batteries and cause the battery insecurity; infinite volume change of lithium anode occurs during charge-discharge


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process which may destroy the electrode structure and lead to poor cycle performance; in addition, the effective anode area contacting electrolyte is limited which restrict the lithium plating/stripping process.9-14 Many researchers have paid their efforts to investigate the protection of Li anode during the past 40 years.15-17 For liquid electrolyte, lots of chemical and electrochemical stable Li salts, solvents and electrolyte additives have been explored to stabilize SEI layer and enhance Coulombic efficiency.18-23 Solid state electrolyte is another effective method to protect Li-anode by mechanically suppressing Li dendrite.24, 25 For interlayer, one adopted method is to fabricate artificial SEI film.26, 27 Functionalizing separator is another pattern to solve the weakness of conventional interlayer.28-30 But these strategies are not directly aimed at the lithium anode itself. In recent years, lithium anode design has come into sight of the researchers.31-34 For designing Li metal anode, a functional host for Li plating/striping have attracted vast attention because it can control Li in a special area to avoid internal problems like volume change, infinite side reaction, SEI cracking, Li dendrite and so on.35-40 Hu’s group designed a 3D carbon nanotube sponge (CNTS) to storage Li, the high specific surface area and excellent electrical conductivity of CNTS evidently promoted uniform Li plating/striping process.41 In another study of Hu’s Group, they designed a composite Li anode by using carbon nanofibers (CNFs) anchoring silver nanoparticles (AgNPs) to direct the deposition of Li metal.32 Guo’s group proposed a new pathway by using graphitized carbon fibers (GCF) as an aggregation of electrode and current collector. The multifunctional GCF exhibited ultrahigh areal density of 8 mA h cm-2 and reliable cyclic property.42 Cui’s group developed a hollow nanocapsules with Au seeds for Li deposition. Through binary phase diagrams analysis, they found Au, Ag, Zn, or Mg have no overpotential to nucleate Li metal on them.43 Substrates made of these metals could restrain Li dendrites during Li nucleation process. Although there have been tremendous efforts to optimize lithium anode design, some important issues are still needed to be addressed toward future practical



application. For example, the various carbon materials used in Li anode design such as carbon nanotube, carbon nanofibers, or carbon materials with special morphologies have high costs and complex preparation processes that greatly hinder their commercialization. More importantly, the design of lithium anode is mainly carried out at the microstructure level, which has high tortuosity in the macrostructure. Actually, the steady 3D structure with open and elongated microchannels may be a good choice for lithium host.44-46 Zhang et al used a carbonized wood with wellaligned channels as Li host material. In this work, they infused molten lithium into the straight channels and discovered that the channels of carbon frame can guide Li stripping/plating process and avoid the volume change.33 Inspired by these wonderful work, we designed a wood-derived host which coordinated with silver nanoparticles as Li composite anode. The carbon material derived from natural basswood was used as the matrix and the Ag nanoparticle was introduced as nucleation seeds to fabricate a new composite host for Li plating and stripping. Li was introduced into the host by electrodeposition which can well control the lithium deposition process during the manufacture of the composite anode. Due to the excellent conductivity of framework and the outstanding lithiophilicity of Ag seeds, this composite structure can promote Li plating/stripping process and avoid Li dendrites. EXPERIMENTAL SECTION Methods. In this work, to prepare wood derived carbon (WDC) and Ag-WDC, the basswood was cut into slices with cross section first. Then, the slices were precarbonized in muffle furnace at 200 ℃. After that we put this film into tube furnace to carbonize at 1000 ℃ under argon atmosphere. Later, the carbonized wood slice was polished by 1000 mesh sandpaper and the wood derived carbon (WDC) was fabricated successfully. To obtain Ag-WDC material, certain amount of silver nitrate was dissolved in distilled water to form a solution. Immerse the WDC in silver nitrate solution over 12 hours. Sodium borohydride was used to reduce silver nitrate. As a result, the nanometer silver was seeded in the channel of WDC. Preformed Ag-WDC


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was cut into 8mm*8mm*0.8mm and heat it at vacuum drying oven no more than 40℃, about 12 h. After that, the Ag-WDC material has been finished. To investigate the cycle performance of two electrodes, we sealed them with 1 M LiPF6 (EC/DEC 1:1) electrolyte, polypropylene separator, and a counter electrode of lithium foil in 2016-type coin cell. This process was conducted in glove box. Later step we employed Neware battery test system to research the electrochemical performance of batteries. The operation temperature is 25℃ and we carried a current density of 5 mA cm-2 to discharge the batteries 10 h for storing Li. Then, cycled them a few times with a current of 0.5 mA cm-2 to solid the SEI and began the cycling with a current of 1 mA cm-2 and a fixed capacity of 1 mA h cm-2. A current of 3 mA cm-2 and a fixed capacity of 3 mA h cm-2 was also employed to test the performance of Ag-WDC electrode in high current density. Further full cell test was conducted to explore their cycle performance. LiFePO4 was used as cathode, and Ag-WDC, WDC and Li foil were used as anode respectively. After deposition Li in the wood derived electrodes, it will be disassembled at glove box and then pack with LiFePO4 cathode. The other battery materials or test instruments we used was the same as above. As for LiFePO4 cathode, firstly commercial LiFePO4 powder were mixed with PVDF (polyvinylidene fluoride) and acetylene black at a mass ratio of 8:1:1. The solvent is N-methyl-2-pyrrolidone (NMP). Then, the mixture was cast on Al foil. After a series of operations, the average mass of LiFePO4 electrode was about 3.5 mg cm−2. Characterization and measurements. To lucubrate the morphology variations of electrodes, the cells were disassembled in glove box. Soon, the electrodes were washed by DEC and cut into small pieces for SEM (HITACHI SU8220) test. The last step should be carried as soon as possible to avoid oxidation. TEM (JEM-2100F) and XRD (Bruker D8 ADVANCE) are also used to explore the property and structure of the



pristine materials. The ionic conductivity was measured by IM6e frequency analyzer (zahner). The sweeping frequency was set from 1M Hz to 0.1Hz and the amplitude was controlled at 5 mA. There is an equation to calculate the ionic conductivity (σ) of electrodes which include other factors like the electrolyte/electrode/membrane resistance (Rs), the electrolyte/membrane resistance (R0), the thickness of wood carbon (d) and the area of wood carbon (S). Following the equation: σ = d / (Rs – R0)A

RESULTS AND DISCUSSION The mechanism of the wood-derived lithium anode for Li metal batteries was illustrated in Figure 1. Natural basswood was used to manufacture composite anode. Basswood slices (Figure S1a) were obtained by cutting perpendicularly to the growth direction, and then were carbonized at 1000 oC for 6 h to improve the electrical conductivity (Figure S1b). The carbon matrix preserves the well-aligned elongated microchannels of basswood. Ag nanoparticles then will be anchored in the woodderived carbon frame. Later lithium was deposited on the channel walls to obtain a composite anode. By electrolytic deposition, Li grows along the channel walls in this composite structure. There are several merits for using silver wood-derived electrode (Ag-WDC) as anode. Firstly, the massive open channels structure of wood-derived carbon matrix can provide inside room for Li growing, and can greatly lessen the volume effect during lithium plating and stripping. Secondly, highly dispersed Ag seeds in channel walls can regulate Li deposition behaviors. Due to the effects of uniformly distributed electrons and less impedance of nucleation, Li metal prefers to deposit and grow around silver nanoparticles and dendrites can be restrained during a long-term


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cycle. Thirdly, the low-tortuosity and aligned microchannels can expedite lithium plating and stripping through the entire anode and enlarge the contact area between lithium and electrolyte during electrode process. Figure 2 is the characterization of WDC and Ag-WDC. After carbonization and polishing treatment, a 3D wood host was fabricated (Figure 2a). Then, Ag nanoparticles were introduced in the carbon matrix to serve as nucleation of Li growing. By scanning electron microscopy (SEM), it can be seen dense particles are well distributed in woodderived carbon channels (Figure 2b and 2c). The further Energy Dispersive Spectrometer (EDS) have applied to prove the distribution of Ag element (Figure 2d). The red dot in Figure 2e apparently indicate the uniform load of nano Ag in channel, and the green area in Figure 2f represent C element. The transmission electron microscopy (TEM) image further confirms the uniform distribution of Ag nanoparticles with an average diameter about 15 nm (Figure 2g). The high resolution transmission electron microscopy (HRTEM) image reveal the 111 plane of nanoparticle Ag with a spacing of 0.23 nm, indicating a good crystallinity (Figure 2i). Later, this composite wood will be fixed into proper size for next battery measurement, and carbonized wood carbon without Ag seeds (WDC) will also be employed for comparative trial under the same condition. Based on previous work, 2016-type coin cells were packed by using the asprepared carbon matrix and lithium foil as electrodes. In order to study the electrochemical performance, the cells were discharged to plate lithium in the beginning at a current density of 5 mA cm-2 and a capacity of 50 mA h cm-2. Then the cells were charged/discharged at a current density of 1 mA cm-2 and a fixed capacity of 1 mA h cm-2 to evaluate the cycling performance. After doing these, scanning electron microscope (SEM) was applied to study the morphology change of Ag-WDC and WDC electrodes at different stages. Figure 3a and 3b show the inside channel images of Ag-WDC electrode after electro-deposition. It can be observed that lots of semi-spheres grow on the channel



walls. The channel morphologies of Ag-WDC electrode after 200 hours cycling show in Figure 3d and 3e. Compared with Figure 3a and 3d, there is no obvious change after such long-term plating/striping, which indicates Ag-WDC composite anode restrained lithium dendrite formation. To further study the mechanism of no dendrite formation, the WDC anode without Ag nanoparticles was investigated. Figure 3c and 3f exhibit WDC electrode’s channel images at deposition stage and after 200 hours cycling respectively. From Figure 3c, it can be seen that Li evenly cover the channels walls after 12 h deposition. No semi-spheres were found and the channels walls were flatter than Ag-WDC. But after 200 h cycling, the matrix channels were crammed by numerous Li dendrites, while the channel with silver nanoseeds still remain its origin morphology. From these results, it can be deduced that Ag nanoparticles play an important role in restraining dendrites formation. The zero overpotential of Li nucleation on Ag nanoparticles makes Li evenly deposit around Ag and form semisphere structure, which is harmless to the anode structure. These evidences prove the importance of silver nanoseeds in stabilizing Li plating/striping process for using AgWDC as Li metal anode. Figure 3g and Figure S5 were the top surface images of AgWDC and WDC electrode just after deposition, respectively. However, their top surface images also displayed obvious difference after 200 hours at a fixed capacity of 1 mA h cm-2. Ag-WDC electrode in Figure 3h still remain the open channel structure while WDC electrode in Figure 3i shows a completely coverage surface morphology. XRD tests of the composite anode are conducted after the 200th plating (Fig. S6). Only lithium peaks are found in XRD, which indicates no degradation products form. In order to better understand the Li nucleation and growth behavior, the detailed SEM images of Li plating/striping process have also been shown in Figure S7. It can be seen that more and more semi-spherical lithium deposit on the channel walls with the increase of plating time and semi-spherical lithium decrease with the increase of stripping time. The images clearly show the Li growth behaviors on Ag-WDC. We presume the inside silver nanoseeds facilitated the uniform deposition of lithium on Ag-WDC while WDC electrode deposit unrestrained which often cause severe dendrites. These variations can confirm the role of silver nanoseeds in wood derived electrode solidly.


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The electrochemistry measurements are also indispensable in assessing the performance of these two wood derived electrodes. Herein, the cycle performances of electrodes were shown in Figure 4. At the initial cycling stage, it can be seen the two electrodes have a nearly equal voltage about 30 mV at the left inset picture. However, their cycling curves have a sharp difference after a long period of electrochemical testing. The black curve which represent WDC electrode reflected a dramatic voltage decrease down to -0.9 V after cycling cell 80 h while the Ag-WDC electrode still showed a steady voltage over 450 h at a current density of 1 mA cm-2 and a fixed capacity of 1 mA h cm-2. Moreover, when the current density of Ag-WDC battery rises up to 3 mA cm-2, the red line which represent Ag-WDC battery at high current density still have a stable voltage curve over 300 h. Figure S4 reveal the impendence spectrum of Ag-WDC and WDC electrode at just deposition stage and 200 hours cycling. As shown in picture, the red line stands Ag-WDC electrode and it increases a small impendence value from 23 Ω to 35 Ω. However, the green lines which stand WDC increase a large value from 32 Ω to 130 Ω. The drastic change of WDC electrode in impendence comes from the frequent side reaction occurring in wood channel. These results stressed the role of nano Ag in wood derived electrode and suggested a new method for designing stable lithium anode was developed successfully. Further full cell test was conducted to explore their cycle performance. LiFePO4 was used as cathode, and Ag-WDC, WDC and Li foil were used as anode, respectively. Fig. 5a unfolds the charge and discharge profiles of the Ag-WDC@LFP, WDC@LFP and Li foil@LFP at 1C. The discharge specific capacity of these three full cells are 148.5, 144.8, 144.6 mA h g-1, respectively. In addition, Ag-WDC@LFP shows a lower voltage polarization (68.3 mV) than WDC@LFP (71.3 mV) and a much smaller voltage polarization than Li foil@LFP (152.2 mV). This result suggests a highly facile electrochemical reaction and low resistance for the Ag-WDC composite anode, which further verifies that both WDC and Ag nanoparticles play a key role in improving cycling performance. Fig. 5b shows the full cell cycling performance of three different anodes at 1 C. After 200 cycles, the full cell of Ag-WDC@LFP shows the least capacity



decay (from 148.9 to 143.9 mA h g-1), while the attenuation of WDC@LFP and Li foil@LFP are respectively from 143.6 to 131.9 mA h g-1 and 141.2 to 126.0 mA h g-1 at the same cycling condition. Fig. 5c shows a more distinct comparison of the voltage hysteresis between charge and discharge process at 0.2 C, 0.5 C, 1 C, 2 C, and 5 C. Among three cells as shown in Fig. 5c, Ag-WDC@LFP exhibits the lowest voltage hysteresis. The voltage hysteresis changes from 40 mV at 0.2 C to 141 mV at 5 C. However, without the help of Ag nano-seeds, WDC@LFP displays a little higher voltage hysteresis of 43 mV at 0.2 C and an obvious higher voltage hysteresis of 180 mV at 5 C. As for the full cell of Li foil@LFP, it apparently shows a much higher voltage hysteresis than those two cells at the testing rates (from 62 mV to 528 mV). And after an uninterrupted test of 200 cycles, the full cell of Ag-WDC@LFP still maintain the lowest voltage hysteresis of 75 mV at a rate of 1 C, and the other two are 86 mV and 200 mV. Evidently using Ag-WDC as lithium anode is an excellent choice. Figure S8 shows the Coulombic efficiency of the Ag-WDC@LFP, WDC@LFP and Li foil@LFP at the current density of 1 C for 200 cycles. From Figure S8, it can be seen that Ag-WDC@LFP has the highest average Coulombic efficiency, which means the Coulombic efficiency of the composite anode has been improved. The Coulombic efficiency of Ag-WDC@LFP cell at large current densities (up to 5 C) is shown in Figure S9. During continuous test at different large current densities, the Coulombic efficiency is always between 100.0% and 99.5% and hardly affected by current density, even at large current density of 5 C.

CONCLUSION To sum up, we successfully developed a dendrite-free Li composite anode through lithium deposition in WDC frame by the assistance of evenly anchored silver nanoparticles. Li can deposit on the channel walls in a uniform semi-spheres which can avoid dendrites formation in this composite lithium anode. The composite anode can circulate stably without dentrites for more than 100 cycles. In addition, the full cell of


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Ag-WDC@LFP exhibits the smallest voltage hysteresis, the most stable specific capacity, the steadiest Coulombic efficiency through long cycles. These results suggest that WDC is a perfect frame supporter for Li anode design, and loading Ag in WDC could effectively regulate Li nucleation behavior, control morphology of Li plating and make plating process harmlessly to the anode structure. The composite anode can effectively

enhance

the

cycle

performance

and

solve

the

Li

dendrites

problems, which is also expected to offer help for designing anode in other research of storage batteries.

ACKNOWLEDGEMENT This work was supported by the National Key Research and Development Program of China (No. 2018YFB0105502), the National Natural Science Foundation of China (NSFC Project Nos. 21776105, 21776104), and the Natural Science Foundation of Guangdong Province (2016A030313503, 2017A030313068).

ASSOCIATED CONTENT Supporting Information SEM; XRD, EIS, and Coulombic efficiency curves of the samples (PDF).

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Figures

Figure 1. Schematic diagram of dendrite-free Li composite anode with Ag wood-derived carbon (Ag-WDC).



Figure 2. (a) Photo and Scanning electron microscopy (SEM) image of carbonized wood (WDC). (b,c) SEM images of uniform loaded nanosilver seeds in the channel of wood. (d) Channel SEM image of Ag-WDC for Energy Dispersive Spectrometer (EDS). (e,f) Ag and C elemental mapping images of Ag-WDC. (g-i) High resolution transmission electron microscopy (HRTEM) images of nanoparticle Ag with 111 crystal face and a distance of 0.23 nm.


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(a)

(c)

(b)

20μm

1μm

(d)

(e)

(f)

(h)

50μm

20μm

20μm

3μm

(g)

1μm

50μm 50μm

(i)

50μm

Figure 3. Morphology variations between Ag-WDC and WDC at deposition stage and after 100 cycles. The current density is set at 1 mA cm-2 and the fixed capacity is 1 mA h cm-2. (a,b) Channel SEM images of Ag-WDC just after Li deposition. (c) Channel image of WDC just after Li deposition. (d,e) Channel SEM images of Ag-WDC after finishing the 100th plating. (f) Channel image of carbonized wood after finishing the 100th plating. (g) Surface SEM images of Ag-WDC after Li deposition. (h) Surface SEM images of Ag-WDC after finishing the 100th plating. (i) Surface SEM images of WDC after finishing the 100th plating.



0.8 0.2

0.2

0.2

0.0

0.0

0.0

0.4 -0.2 0

1

2

3

-0.2 144

(h)

145

146

147

-0.2 450

(h)

451

452

453

(h)

0.0

Voltage (V)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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Ag-WDC 1 mA cm-2, 1 mA h cm-2 WDC 1 mA cm-2, 1 mA h cm-2

-0.4 0

0.2

50

100

Ag-WDC 3 mA

150

cm-2,

200

3 mA h

250

300

350

400

450

cm-2

0.0 -0.2 0

50

100

150 Time (h)

200

250

300

Figure 4. Electrochemical performance of the Ag-wood derived carbon (Ag-WDC) and the woodderived carbon (WDC). The corresponding current density are 1 mA cm-2 and 3 mA cm-2 and the fixed capacity are 1 mA h cm-2 and 3 mA h cm-2.


(a)

Voltage (V)

4.5 4.0

68.3 mV 71.3 mV 152.2 mV

1C

3.5 Ag-WDC@LFP WDC@LFP Li foil@LFP

3.0 2.5 0

0.6 Voltage hysteresis (V)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Specific capacity (mAh g-1)

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50 100 Specific capacity (mA h g-1)

150

(b)

200

1C

150 100

Ag-WDC@LFP WDC@LFP Li foil@LFP

50 0

0

50

5C

(c)

100 Cycle number

150

200

Ag-WDC@LFP WDC@LFP Li foil@LFP

0.4

2C 0.5 C

0.2 C 0.0

1C

1C

0.2

0

5

10

15

20

25 40 Cycle number

80

120

160

200

Figure 5. Full cell performance of the Ag-WDC@LFP, WDC@LFP and Li foil@LFP. LFP represents LiFePO4 cathode. (a) The charge and discharge profiles of three kinds of LFP full cells using different anodes at 1 C (1 C equal to 170 mA g-1). (b) Full cell cycling performance of three different anodes at 1 C. (c) Comparison of the median voltage hysteresis of charge and discharge at 0.2 C, 0.5 C, 1 C, 2 C, and 5 C.



Table of Contents Graphic


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Dendrite-Free Composite Li Anode Assisted by Ag Nanoparticles in a

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