S-1

Supporting Information

Hyperbranched Triphenylamine Polymer for Ultrafast Battery Cathode.

Keiichi Yamamoto*, Daichi Suemasa, Kana Masuda, Kazunari Aita, Takeshi Endo

† Advanced Materials Research Laboratories, JSR Corporation, 100, Kawajiri-cho, Yokkaichi,

Mie,510-8552, Japan

‡ Molecular Engineering Institute, Kindai University, 11-6, Kayanomori, Iizuka, Fukuoka, 820-8555,

Japan

E-mail address: Keiichi_Yamamoto@jsr.co.jp

KEYWORDS

Triphenylamine polymer, Hyperbranched polymer, ultrafast battery, Long cycle life, Organic-LFP

hybrid cathode, Organic-inorganic charge transfer

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Table of Contents

1. Chemicals and general methods

2. Synthesis of PHTPA

3. Characterization of PHTPA

4. Cell fabrication

5. Charge-discharge test method

6. XRD pattern of cathodes

7. SEM images

8. DC-IR measurement

9. Electrochemical Impedance Spectroscopy (EIS)

10. Warburg coefficients

11. Cycle performance of PHTPA-LFP hybrid cathode

12. Reaction equation of charge-discharge reaction on cathode

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1. Chemicals and general methods

All chemicals were used as received without any further purification. Bis (4-

bromophenyl)amine, diphenylamine, bis(tri-t-butylphosphine) palladium (0) and all

solvents were purchased from Wako Pure Chemical Industries, Ltd., sodium tert-butoxide

was from Tokyo Chemical Industry Co., Ltd.. As for an electrolyte, 1M LiPF6, EC/DEC

(30/70) was purchased from Kishida Chemical Co., Ltd.. LFP active material was

purchased from Johnson Matthey Co. Ltd. (the grade name is Life power-P2). Acetylene

black (HS-100, Denka Co., Ltd.) and SWCNT (TUBALL, OCSiAl) was used as an

electro-conductive agent. PVdF (Mw 530,000, Sigma-Aldrich Co., Ltd.) was used as a

binder material. GA100 glass fiber filter (Advantech Co., Ltd.) was used as a separator of

a cell. Typical PTPA was synthesized by the same method described in the literature. (6f)

1H-NMR spectrum was recorded on JEOL 400MHz spectrometer at room temperature

using CDCl3 as a solvent and TMS as the standard. FT-IR spectrum was recorded on

Thermo Scientific Nicolet iS10 FT-IR with diamond ATR. The polymer weight vs

polystyrene standard was determined on TOSOH HCL-8320GPC with TSKgelsuper HM-

H as the column using THF as the eluent. The mass of repeat unit was determined on

MALDI-TOFMS (Shimadzu, AXIMA Confidence) using 1,8,9-anthracenetriol and

sodium trifluoroacetate as the matrix and THF as the solvent. The charge-discharge

performances were measured by TOSCAT 3100 (TOYO-SYSTEM Co., Ltd.) and VMP3

(Bio-Logic Co., Ltd.) at 25 °C. For EIS measurement, Warburg impedance and Diffusion

coefficient, VMP3 (Bio-Logic Co., Ltd.) was used at 25 °C. XRD pattern of cathodes

were recorded on Rigaku SmartLab with Cu Kα radiation. SEM images were recorded

on JSM-6010LA (HITACHI).

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2. Synthesis of PHTPA

Scheme S1. Synthesis of Poly Hyperbranched Triphenylamine (PHTPA).

PHTPA was synthesized by co-polymerization of diphenylamine and Bis (4-

bromophenyl) amine shown in the chemical equation of scheme S1. The polymerization

was carried out under inert atmosphere using standard Schlenk techniques. Bis (4-

bromophenyl) amine of 3.27g (10mmol) , diphenylamine of 1.69g (10mmol) , sodium

tert-butoxide of 2.88g (30mmol) and toluene of 10ml were added to 100ml flask. The

mixture was stirred at r.t. for 30min, followed by addition of bis (tri-t-butylphosphine)

palladium (0) of 5mg (0.01mmol) as the catalyst. The resulting mixture was allowed to

stir at 100 °C for 6hrs. After reaction, the reaction mixture was washed twice with

distilled water of 30ml to remove a byproduct NaBr. The organic phase was separated,

and was poured into methanol of 50ml to remove the residual catalyst and monomers. The

obtained pale-green powder was dried at 60 °C in vacuum for 24hrs. PHTPA dry powder

was obtained (3.3g, 99% yield).

3. Characterization of PHTPA

Figure S1.

1H-NMR (400MHz) spectrum of PHTPA in CDCl3.

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Figure S2. FT-IR spectrum of PHTPA.

Figure S3. GPC trace of PHTPA in THF.

Figure S4. MALDI-TOFMS spectrum of PHTPA cast film from THF solution.

MALDI-TOFMS

168.24

165.96

168.26

166.14

168.12

334.4 334.86

334.39 334.51

166.2

168.07

166.32

168.00

166.51 167.77

FW=166 FW=168

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4. Cell fabrication

Fabrication of cathode

0.4g of PHTPA, 0.5g of acetylene black, 1.25g of PVDF 8wt% NMP solution (Electrode

weight ratio = 4/5/1) and 2g of an additional NMP were added into 20ml polyethylene

(PE) cup. 12g of 5mmφzirconia beads were used as the grinding media. The mixture was

mixed at r.t. for 50min, followed by the coating on Al current collector. The coated foil

was dried on a hot-plate at 100 °C for 20min, and then was dried in a vacuum chamber at

100 °C for 9hrs. The resulting electrode was cut to the desired size, and was used as the

cathode.

Fabrication of Cell

CR-2032 coin type cell was used. 1M LiPF6, EC/DEC (30/70) for the electrolyte, Li foil

for the anode, GA100 glass fiber filter for the separator were used as shown below.

Figure S5. Cell configuration used.

5. Charge-discharge test method

For Figure 1 (Charge-discharge curves and rate capability of PHTPA),

Cut off voltage: 4.2-2.0V, Charging mode and C-rate：CC, 0.5 C～300C.

For Figure 2 (Long life cycle performance of PHTPA),

Cut off voltage: 4.0-2.8V, Charging mode and C-rate：CC, 20C or 100C.

For Figure 5 (Rate capability and charge-discharge curves of PHTPA-LFP hybrid ),

Cut off voltage: 4.0-2.8V, Charging mode and C-rate：CC, 0.1 C～100C.

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6. XRD pattern of cathodes

After charging, the cathode was removed from the cell, and was washed by acetone.

After drying, XRD pattern of the cathode was measured with a transmission method.

Figure S6. X-ray diffraction (XRD) pattern of hybrid cathode uncharged (a), charged at

100C-rate (b), charged at 1C-rate (c).

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7. SEM images

SEM images were recorded on JSM-6010LA (HITACHI). The specimens were prepared

by dissolving the polymer in NMP and baking at 100 °C on a hot-plate for 20min.

Figure S7. SEM images of the film made from PHTPA and PVDF (PHTPA:PVDF=40:10)

(a), and the film made of only PHTPA (b).

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8. DC-IR measurement

DC-IR values were calculated from the slope of a plot of the current I VS v delta (IR drop)

during charge or discharge at SOC=0% or 100% respectively.

Figure S8. Relation between charge-discharge current and IR-drop.

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9. Electrochemical Impedance Spectroscopy (EIS)

The test cells were newly prepared and were measured after charging to SOC of 50%.

Figure S9. Nyquist-plot for PHTPA (a), Typical PTPA (b), LFP(C), Hybrid PHTPA-LFP

(PHTPA:LFP=20:80) (d) measured at SOC50%.

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10. Warburg coefficients

Warburg coefficients (σ) were estimated from the slope of a plot of the Re (Z) vs the

square root of frequency (ω1/2) obtained from EIS measurement.(Figure. S9)

Figure S10. Warburg plot for PHTPA and Typical PTPA (a) and LFP and Hybrid PHTPA-

LFP (PHTPA:LFP=20:80) (b) calculated from EIS measurement (Figure. S9).

Table S1. Results of Warburg coefficients.

Sample Warburg coefficient

PHTPA 8.4 Typical PTPA 22.7 LFP 32.7 Hybrid PHYPA-LFP(20-80) 11.8

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11. Cycle performance of PHTPA-LFP hybrid cathode

Figure S11. Cycle performance for PHTPA-LFP(20:80) Hybrid (a) and only LFP (b).

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12. Reaction equation of charge reaction on cathode

(a) LFP direct charging (with high Rct and high Warburg coefficient)

(b) PHTPA charging (Fast charging, with high Rct and low Warburg coefficient)

(c) PHTPA+ PF6

- salt charges LFP (charge transfer step, the Rct should be zero)

Figure S12. Reaction equation of charge reaction for LFP charging directly (a) and PHTP

charging (b) and charge transfer step (c).

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