Compound HBQP: Hydroquinone-formaldehyde polymer was synthesized

according to the following procedure [40]: hydroqui- none (8.80 g, 80 mmol) and
37 wt. % formaldehyde (16.0 mL, 215 mmol) were dissolved in a mixture of 30
mL of ethanol and 2.8 mL of concentrated hydrochloric acid in a 150 mL autoclave
with a Teflon lining. The autoclave was then sealed and heated in an oven at 120 C
for 24 h. The resulting black gel was ground and soaked in 50 g of stirred ethanol
for 12 h. Finally, the slurry was filtrated and washed with ethanol. The filter cake
was air-dried to a state that had an ethanol content of about 80 wt. %. Then, the friable
filter cake was ground into powder and further dried at 120 C in a flow of nitrogen
to get dark brown powder (11.46 g, 107% yield).
Compound BQP: Quinone-formaldehyde polymer was obtained using a
modified procedure [41]. Compound HBQP (2.68 g, 20 mmol) was finely
ground in a mortar and then suspended in 60 mL MeOH using ultrasonic bath for ½
h. Then 1.5 mL 37 wt. % HCl was added, followed with 30 wt. % hydrogen peroxide
solution in water (4.4 mL, 44 mmol) and iodine (0.128 g, 0.5 mmol) as a catalyst.
Reaction mixture was then stirred for 3 days at RT and the colour was changed from
dark brown to orange brown. To improve the yield another portion of hydrogen
peroxide was added and stirred for additional 1 day. Then the suspension was
filtrated and the fuming cake was resuspended in fresh MeOH for 15 min using
ultrasonic bath. After filtration the cake was first dried at 50 C (2 h, air) and then
under high vacuum (overnight, RT) obtaining an or- ange brown powder (2.84 g,
108% yield).
Infrared spectroscopy: IR spectra were measured on a FTIR
spectrophotometer Bruker IFS66/S using a KBr pellet.

Nuclear magnetic resonance (NMR): 1H-13C CPMAS NMR spectra were

recorded on a 600 MHz Varian system equipped with a 3.2 mm Varian NB Double
Resonance HX MAS probe. Larmor frequencies were 599.601 MHz and 150.785
MHz for 1H and 13C nuclei, respectively. Chemical shifts were reported relatively
to the signals of 13C nuclei in tetramethylsilane. Sample rotation fre- quency was
16 kHz and relaxation delay was 5 s. Polarization transfer was achieved with
RAMP cross-polarization [42] (ramp on the proton channel) with contact time of
5 ms. High-power XiX heteronuclear proton decoupling was applied during
acquisition [43].
Pyrolisis: Pyromat Manual Curie-point was used to determine polymer
composition at 650 C for 10s. Degradation products were separated in an Agilent
Technologies 6890 N gas chromatograph. The following temperature program was
used: 40 C for 2 min and then 10 C/min till 300 C. A 25 m 0.2 mm HP-5
column and helium as a carrier gas were used. For determination of the prod- ucts
mass selective detector Agilent Technologies 5973 N was used using NIST database
with 80% matching.
 TGA-MS analysis: Thermogravimetric measurements were performed on a
Netzsch 449 F3 Jupiter instrument under a dynamic Ar (5.0) flow with a flow rate of
60 mL/min in a temperature range from 25 to 900 C. A heating rate of 10 K/min
was used. About 50 mg of sample was placed in an alumina (Al2O3) crucible.
Simultaneously mass spectrometry was performed on MS 403C Ae€olos with a
SEM Chenneltron detector and a system pressure of 2 105 mbar. Gasses that evolved
under TGA heat treatment were transferred to the mass spectrometer through
transfer capillary, quartz ID 75 mm, which was heated up to 220 C. The upper limit
of the mass spectrometer detector was 100 AMU.
Iodine Starch test: 30 mg of powdered sample BQP was sus- pended in a
solution of 120 mg potassium iodide in 2 mL distilled water. The mixture was heated
up to 90 C under inert atmosphere (to prevent air oxidation of iodide anion to
iodine) and stirred for 3 h to extract as much iodine from BQP as possible. Then
suspen- sion was filtrated, resulting in a colourless filtrate to which 0.2 mL of 1 wt.
% starch solution was added. Only very weak coloration appeared indicating a very
low iodine content. To measure the iodine concentration, titration with a 0.0127
M Na2S2O3 solution was carried out. 8 mg of this solution already caused
discoloration indicating that less than 0.04 wt. % iodine was present in BQP.
Elemental analysis: For elemental analysis instrument 2400 Series II
CHNS/O (Perkin Elmer) was used, coupled with automatic microscale AD-6
Autobalance. For oxidation, pure oxygen (>99,999%) was used, the heating
temperature was >1800 C. Oxidation gases were separated using frontal
chromatography. Separated gases were analyzed and measured with the thermal
conductivity method.
X-ray diffraction (XRD): Instrument PAN analytical X'Pert PRO MPD was
used using wavelength CuKɑ1 ¼ 15,406 Å. Silicon sample holder was used and
measured angle was between 5 and 65o.
Scanning electron microscopy (SEM) was performed on a Carl Zeiss FE
SEM Supra 35 VP instrument using 1 kV. Chemical composition was determined
by electron energy dispersive analysis (EDX or EDS) using 20 kV.
Transmission electron microscopy (TEM) was performed on aJeol, model
ARM 200C instrumen.
BET nitrogen adsorption: Micromeritics ASAP 2020 instrument with V3.04
G software was used. The nitrogen isotherms were measured at 77 K. The
samples were degassed at 393 K and pressure less than 26 Pa for 12 h was used.
The specific surface area was calculated using the Brunauer-Emmett-Teller (BET)
method based on adsorption data in the partial pressure (P/Po) range 0.05x0.20,
and total pore volume was determined from the amount of nitrogen adsorbed at P/Po
¼ 0.98. Assembling batteries: Electrodes were prepared by mixing 40 mg of
active compound, 40 mg of carbon black (Printex) and 20 mg of PTFE (60 wt. %
water dispersion, Aldrich) and 0.7 mL of isopropyl alcohol (IPA). All these
ingredients were ball milled in 12 mL stainless steel grinding jars (using 5 5
mm balls) with planetary ball mill (RETSCH PM100) at 300/min for 30 min in air
atmosphere. The obtained slurry was kneaded with a mortar and pestle to get a
compact black gum. The gum was then applied on an Aluminium foil (0.02 mm thick)
with a roller to get approximately 6 6 cm of Al surface covered with electrode
composite. The Al foil was previously brushed with a sandpaper (800 mesh) and
washed several times with EtOH. Then Al covered with electrode composite was let
to dry in air atmosphere. Then a pressure of 15 t was applied to the whole surface.
After that electrode discs of 1.2 cm in diameter were cut out and pressed with 5 t
again. These electrodes were then dried at 80 C in vacuum for 1 day. Battery cells
were assembled in a glove box (water and oxygen levels < 1 ppm). Then Swagelok
type battery cells were made using the above-mentioned electrodes, a 13 mm
glassy fiber separator (Whatman GF/A) and freshly rolled lithium (12 mm diameter,
Aldrich). For every cell 5 drops of elec- trolyte was used. Different electrolytes
were used: 1 M LiPF6/ EC þ DEC ¼ 1:1 (vol.) (Ethylene carbonate þ Diethyl
carbonate), 1 M LiTFSI/DOL þ DME ¼ 1:1 (vol.) (1,3-Dioxolane þ Dimethoxyethane),
1 M LiTFSI/TEGDME (Tetraethylene glycol dimethyl ether), 1 M LiClO4/GBL (Gama-
butyrolactone).
Electrochemical measurements were performed on a VMP3 potentiostat/
galvanostat (Bio-Logic, France) at room temperature (25 C). Batteries were cycled
with different current densities: 20, 40 and 50 mA/g (see the corresponding main
text). The rate capa- bility test was carried out in a wide range - from 20 mA/g
till 1620 mA/g. Two different voltage windows were used: 1.5e3. V and 1.5e3.5
V. All potentials are versus metallic lithium. Cyclic voltammetry measurements
were performed in a two-electrode cell with a scan rate of 0,1 mv/s.
 Senyawa HBQP: polimer Hydroquinone-formaldehida disintesis sesuai dengan prosedur
berikut [40]: hydroqui- none (8,80 g, 80 mmol) dan 37 wt. % formaldehida (16,0 mL, 215 mmol)
dilarutkan dalam campuran 30 mL etanol dan 2,8 mL asam hidroklorat pekat dalam autoklaf 150
mL dengan lapisan Teflon. Autoklaf kemudian disegel dan dipanaskan dalam oven pada 120 C
selama 24 jam. Gel hitam yang dihasilkan digiling dan direndam dalam 50 g etanol yang diaduk
selama 12 jam. Akhirnya, bubur disaring dan dicuci dengan etanol. Cake filler dikeringkan sampai
keadaan yang memiliki kandungan etanol sekitar 80% berat. % Kemudian, kue filler yang gembur
digiling menjadi bubuk dan dikeringkan lebih lanjut pada 120 ° C dalam aliran nitrogen untuk
mendapatkan bubuk coklat gelap (11,46 g, hasil 107%).
Compound BQP: Quinone-formaldehyde polymer diperoleh menggunakan prosedur
yang dimodifikasi [41]. Senyawa HBQP (2,68 g, 20 mmol) ditumbuk halus dalam mortar dan
kemudian disuspensikan dalam 60 mL MeOH dengan menggunakan ultrasonic bath selama ½
jam. Kemudian 1,5 mL 37% berat. % HCl ditambahkan, diikuti dengan 30% berat. % larutan
hidrogen peroksida dalam air (4,4 mL, 44 mmol) dan yodium (0,128 g, 0,5 mmol) sebagai katalis.
Campuran reaksi kemudian diaduk selama 3 hari di RT dan warnanya berubah dari coklat gelap
menjadi coklat oranye. Untuk meningkatkan hasil, bagian lain dari hidrogen peroksida
ditambahkan dan diaduk selama 1 hari tambahan. Kemudian suspensi disaring dan kue yang
marah diresuspensi dalam MeOH segar selama 15 menit menggunakan mandi ultrasonik. Setelah
filtrasi, kue pertama dikeringkan pada 50 C (2 jam, udara) dan kemudian di bawah vakum tinggi
(semalam, RT) memperoleh bubuk coklat orange (2,84 g, hasil 108%).
Spektroskopi inframerah: Spektrum IR diukur pada spektrofotometer FTIR Bruker IFS66
/ S menggunakan pelet KBr.
Nuclear magnetic resonance (NMR): Spektrum 1H-13C CPMAS NMR direkam pada
sistem Varian 600 MHz yang dilengkapi dengan probe Varian NB Double Resonance HX MAS 3,2
mm. Frekuensi Larmor adalah 599.601 MHz dan 150.785 MHz untuk 1H dan 13C inti, masing-
masing. Pergeseran kimia dilaporkan relatif terhadap sinyal dari 13C inti dalam tetramethylsilane.
Frekuensi rotasi sampel adalah 16 kHz dan penundaan relaksasi adalah 5 detik. Transfer polarisasi
dicapai dengan polarisasi-silang RAMP [42] (ramp pada saluran proton) dengan waktu kontak 5
ms. Daya tinggi Xion proton heteronuklear decoupling diterapkan selama akuisisi [43].
Pyrolisis: Pyromat Manual Curie-point digunakan untuk menentukan komposisi polimer
pada 650 C selama 10 detik. Produk degradasi dipisahkan dalam kromatografi gas Agilent
Technologies 6890 N. Program temperatur berikut ini digunakan: 40 C selama 2 menit dan
kemudian 10 C / menit sampai 300 C. Sebuah kolom HP-5 0,2 m dan 25 mm dan helium sebagai
gas pembawa digunakan. Untuk penentuan detektor selektif massa produk, Agilent Technologies
5973 N digunakan menggunakan basis data NIST dengan pencocokan 80%.

Analisis TGA-MS: Pengukuran Thermogravimetri dilakukan pada instrumen Jupiter

Netzsch 449 F3 di bawah aliran Ar (5.0) dinamis dengan laju aliran 60 mL / menit dalam rentang
suhu dari 25 hingga 900 C. Tingkat pemanasan 10 K / min digunakan. Sekitar 50 mg sampel
ditempatkan dalam wadah alumina (Al2O3). Spektrometri massa secara bersamaan dilakukan
pada MS 403C Ae € olos dengan detektor SEM Chenneltron dan tekanan sistem 2 105 mbar. Gas
yang berevolusi di bawah perlakuan panas TGA dipindahkan ke spektrometer massa melalui
transfer kapiler, kuarsa ID 75 mm, yang dipanaskan hingga 220 C. Batas atas detektor
spektrometer massa adalah 100 AMU.
Uji Iodine Starch: 30 mg sampel bubuk BQP ditimbang dalam larutan 120 mg kalium
iodida dalam 2 mL air suling. Campuran dipanaskan hingga 90 ° C di bawah atmosfir inert (untuk
mencegah oksidasi udara dari anion iodida ke iodin) dan diaduk selama 3 jam untuk mengekstrak
sebanyak yodium dari BQP sebanyak mungkin. Kemudian suspensi disaring, menghasilkan fi ltrasi
tak berwarna hingga 0,2 mL 1% berat. % larutan pati ditambahkan. Hanya pewarnaan yang sangat
lemah yang menunjukkan kandungan yodium yang sangat rendah. Untuk mengukur konsentrasi
yodium, titrasi dengan larutan Na2S2O3 0,0127 M dilakukan. 8 mg larutan ini sudah
menyebabkan perubahan warna yang menunjukkan kurang dari 0,04% berat. % yodium hadir di
BQP.
Analisis unsur: Untuk instrumen analisis unsur 2400 Seri II CHNS / O (Perkin Elmer)
digunakan, ditambah dengan otomasi AD-6 otomatis skala mikro. Untuk oksidasi, oksigen murni
(> 99,999%) digunakan, suhu pemanasan> 1800 C. Gas oksidasi dipisahkan menggunakan
kromatografi frontal. Gas yang dipisahkan dianalisis dan diukur dengan metode konduktivitas
termal.
Difraksi sinar X (XRD): Instrumen PAN analitis X'Pert PRO MPD digunakan menggunakan
panjang gelombang CuKɑ1 ¼ 15,406 Å. Pemegang sampel silikon digunakan dan sudut yang
diukur adalah antara 5 dan 65o.
Scanning electron microscopy (SEM) dilakukan pada instrumen Carl Zeiss FE SEM Supra
35 VP menggunakan 1 kV. Komposisi kimia ditentukan oleh analisis dispersif energi elektron (EDX
atau EDS) menggunakan 20 kV.
Transmisi mikroskopi elektron (TEM) dilakukan pada instrumen JEol, model ARM 200C.
BET nitrogen adsorpsi: Micromeritics ASAP 2020 instrumen dengan perangkat lunak
V3.04 G digunakan. Isoterm nitrogen diukur pada 77 K. Sampel didesorikan pada 393 K dan
tekanan kurang dari 26 Pa selama 12 jam digunakan. Luas permukaan spesifik dihitung
menggunakan metode Brunauer-Emmett-Teller (BET) berdasarkan data adsorpsi pada tekanan
parsial (P / Po) berkisar 0,05x0,20, dan volume pori total ditentukan dari jumlah nitrogen yang
diadsorpsi pada P / Po ¼ 0,98.
Baterai perakitan: Elektroda disiapkan dengan mencampur 40 mg senyawa aktif, 40 mg
karbon hitam (Printex) dan 20 mg PTFE (60% berat dispersi air, Aldrich) dan 0,7 mL isopropil
alkohol (IPA). Semua bahan ini adalah bola yang digiling dalam guci 12 mL stainless steel
(menggunakan 5 bola 5 mm) dengan planet ball mill (RETSCH PM100) pada 300 / menit selama
30 menit di udara. Bubur yang diperoleh diremas dengan lesung dan alu untuk mendapatkan
getah hitam yang padat. Gusi kemudian diaplikasikan pada aluminium foil (tebal 0,02 mm)
dengan roller untuk mendapatkan sekitar 6 6 cm permukaan Al tertutup dengan elektroda
komposit. Al foil sebelumnya disikat dengan amplas (800 mesh) dan dicuci beberapa kali dengan
EtOH. Kemudian Al yang dilapisi dengan elektroda komposit dibiarkan kering di udara. Kemudian
tekanan 15 t diterapkan ke seluruh permukaan. Setelah itu, cakram elektroda berdiameter 1,2
cm dipotong dan ditekan lagi dengan 5 t. Elektroda ini kemudian dikeringkan pada 80 C dalam
ruang hampa selama 1 hari. Sel baterai dirakit dalam kotak sarung tangan (air dan kadar oksigen
<1 ppm). Kemudian sel baterai tipe Swagelok dibuat menggunakan elektroda yang disebutkan di
atas, pemisah serat gelas 13 mm (Whatman GF / A) dan lithium yang baru digulung (diameter 12
mm, Aldrich). Untuk setiap sel 5 tetes elektrolit digunakan. Elektrolit yang berbeda digunakan: 1
M LiPF6 / EC þ DEC ¼ 1: 1 (vol.) (Etilena karbonat þ Diethyl carbonate), 1 M LiTFSI / DOL þ DME ¼
1: 1 (vol.) (1,3-Dioxolane þ Dimethoxyethane), 1 M LiTFSI / TEGDME (Tetraethylene glycol
dimethyl ether), 1 M LiClO4 / GBL (Gama-butyrolactone).
Pengukuran elektrokimia dilakukan pada VMP3 potensiostat / galvanostat (Bio-Logic,
Perancis) pada suhu kamar (25 C). Baterai didaur ulang dengan kerapatan arus yang berbeda: 20,
40 dan 50 mA / g (lihat teks utama yang sesuai). Uji kemampuan cacah dilakukan dalam kisaran
luas - dari 20 mA / g hingga 1620 mA / g. Dua jendela tegangan yang berbeda digunakan: 1.5e3.
V dan 1.5e3.5 V. Semua potensi versus litium metalik. Pengukuran voltametri siklik dilakukan
dalam sel dua elektroda dengan tingkat scan 0,1 mv / s.