CN112382513B - Preparation method of double-ion water system energy storage device - Google Patents
Preparation method of double-ion water system energy storage device Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002114 nanocomposite Substances 0.000 claims abstract description 16
- 239000004744 fabric Substances 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 13
- 238000004070 electrodeposition Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 11
- 239000010406 cathode material Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000006479 redox reaction Methods 0.000 abstract description 4
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- 238000002484 cyclic voltammetry Methods 0.000 description 11
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- 150000001450 anions Chemical class 0.000 description 2
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- 238000000840 electrochemical analysis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a double-ion water system energy storage device. (1) Carrying out pretreatment such as cleaning on a metal copper sheet, carrying out anodic oxidation under certain conditions, and sintering at high temperature in a tubular furnace to obtain a CuO nano array electrode; (2) the commercial carbon cloth is pretreated by cleaning and the like, and VC/V is obtained through electrochemical deposition, carbon coating and high-temperature carbonization under certain conditions2O3a/C nanocomposite electrode; (3) the two electrodes are separated by a diaphragm and assembled into a water system energy storage device in KOH electrolyte, and the energy storage device has unique dual-ion energy storage characteristics, namely CuO and OH‑Redox reaction, VC/V2O3C and K+And (4) carrying out oxidation-reduction reaction. Therefore, the invention discloses a double-ion water system energy storage device by using a simple preparation method, and the double-ion water system energy storage device has excellent electrochemical performance and has a very good application prospect in electrochemical energy storage devices.
Description
Technical Field
The invention relates to the field of electrochemical energy storage devices, in particular to a preparation method of a double-ion water system energy storage device
Background
With the progress of human science and technology, the consumption of fossil energy has also caused serious environmental problems. Therefore, the development of electrochemical energy storage devices capable of utilizing clean energy has been a hot research. Among them, the water system super capacitor/battery has the advantages of fast charge and discharge speed, long cycle life, low price, etc. and is considered as an ideal energy storage device.
It is known that multi-ion storage can effectively increase the energy density of the device compared with single cation storage (Li, Na, K ions, etc.). However, in an aqueous environment, there is a lack of design related to multi-ion storage devices.
In view of the above, the invention proposes that charge storage is promoted by simultaneously carrying out redox reactions on positive and negative electrode materials and anions and cations of the alkaline electrolyte, so as to realize high specific capacity, thereby significantly improving the energy density of the energy storage device. Therefore, the invention discloses a bi-ionic water system energy storage device by using a method which is simple to operate. The electrochemical performance of the material is excellent, and the material has a very good application prospect in electrochemical energy storage devices.
Disclosure of Invention
The invention provides a design method of a dual-ion water system energy storage device, which can effectively improve the energy storage density of the device. Wherein, store (OH)-) The key cathode materials of the anion can comprise CuO, NiO and Co3O4A mixture of one or more of them.
The invention is realized by the following steps: in an embodiment of the present invention, a method for designing a dual-ion energy storage device is provided, which includes: the anode material is CuO nano array electrode, and the cathode material is VC/V2O3The electrolyte of the/C nano composite electrode is KOH solution. The preparation method comprises the steps of preparing the CuO nano array electrode and VC/V2O3the/C nanocomposite electrode is separated by a separator and assembled in an aqueous electrolyte.
(1) The preparation steps of the anode material CuO nano array electrode are as follows:
a. ultrasonic cleaning a metal substrate in deionized water, an acid solution and ethanol in sequence, and vacuum drying;
b. preparing KOH electrolyte with certain concentration, and preparing a metal hydroxide electrode by a direct-current stable power supply anodic oxidation method;
c. and dehydrating the metal hydroxide by high-temperature sintering under the argon atmosphere to obtain the metal oxide nanowire.
The metal substrate in the step a is a commercial metal copper sheet, the ultrasonic cleaning time is 10-30 min, the vacuum drying temperature is 40-100 ℃, and the drying time is 6-12 h. .
The concentration of KOH in the step b is 2-6M, the anodic oxidation voltage is 1-3V, the time is 20-60 min, the anode in the electrolytic cell is a copper sheet, the cathode is a platinum sheet, and the metal hydroxide is Cu (OH)2The metal oxide is CuO.
And c, preserving the heat at the temperature of 150 ℃ for 3h, and then preserving the heat at the temperature of 200-350 ℃ for 3 h.
(2) The negative electrode material VC/V2O3The preparation steps of the/C nano composite electrode are as follows:
a. ultrasonically cleaning commercial carbon cloth in deionized water, acid solution and ethanol in sequence, and drying in vacuum;
b. preparing VOSO with certain concentration4An electrolyte, which is used for depositing vanadium oxide on the commercial carbon cloth through an electrochemical deposition technology;
c. soaking the vanadium oxide deposited on the carbon cloth in a glucose aqueous solution with a certain concentration for several hours;
d. and carbonizing the surface of the vanadium oxide into vanadium carbide by high-temperature sintering under the argon atmosphere.
In the step a, the ultrasonic cleaning time is 10-30 min, the vacuum drying temperature is 40-100 ℃, and the drying time is 6-12 h.
And b, in a three-electrode system, the working electrode is carbon cloth, the counter electrode is a platinum sheet, and the reference electrode is Ag/AgCl. VOSO4The concentration is 0.5-2M, the electrochemical deposition voltage is 1-3V, and the time is 1-5 min.
The concentration of the glucose aqueous solution in the step c is 1-3M, and the soaking time is 6-12 h.
And d, the high-temperature sintering temperature in the step d is 900-1200 ℃, and the time is 60-120 min.
Through the stationThe electrochemical test method of the double-ion water system energy storage device prepared by the method comprises the following steps: the anode material CuO nano array electrode and the cathode material VC/V2O3the/C nano composite electrode is separated by a diaphragm and assembled into an aqueous energy storage device in 2M KOH electrolyte. The voltage windows of the cyclic voltammetry curve and the charging and discharging curve are 0-1.2V, the scanning rate is changed to obtain the cyclic voltammetry curve under different scanning rates, the area specific capacity of the different scanning rates is calculated, the current density is changed to obtain the charging and discharging curve under different current densities, and the voltage window is 10 DEG5Performing electrochemical impedance spectrum test at HZ-0.01 Hz frequency of 200mV s-1And 10000 cycles of cyclic voltammetry curve tests at the scanning rate and calculates the capacity retention rate, and the relation between the energy density and the power density is calculated according to the electrochemical performance test.
The invention has the beneficial effects that:
the CuO nano array is directly grown on the copper sheet substrate by an anodic oxidation method; preparing VC/V on carbon cloth by electrochemical deposition method and carbon coating technology2O3a/C nano composite electrode. Two electrodes are assembled in KOH electrolyte, and anode is CuO and OH-Oxidation-reduction reaction of (1), negative electrode VC/V2O3C and K+Thereby promoting charge storage and realizing the energy storage characteristic of the double ions. In addition, the two electrode preparation methods do not need secondary preparation of the electrodes and addition of a certain proportion of binders, so that the internal resistance of the electrodes can be effectively reduced. The preparation method is simple, the double-ion energy storage characteristic is realized through the anode and cathode materials and the KOH electrolyte in the charging and discharging processes, and the electrochemical performance is excellent, so that the preparation method has a good application prospect in an electrochemical energy storage device.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a CuO nanoarray as a cathode material;
fig. 2 is a Scanning Electron Microscope (SEM) image of the negative electrode material, in which:
FIG. 2a is V2O3SEM image of/C nanocomposite electrode;
FIG. 2b shows VC/V2O3SE of/C nanocomposite electrodeAn M diagram;
FIG. 3 is an XRD spectrum of a CuO nanoarray as a cathode material;
fig. 4 is an XRD pattern of the negative electrode material, in which:
FIG. 4a is V2O3XRD pattern of/C nanocomposite electrode;
FIG. 4b shows VC/V2O3XRD pattern of/C nanocomposite electrode;
FIG. 5 is a cyclic voltammogram of a bi-ionic water-based energy storage device at different scanning rates;
FIG. 6 is a graph of area to capacity of a dual-ion water system energy storage device at different scan rates;
FIG. 7 is a charge-discharge diagram of a dual-ion aqueous energy storage device at different current densities;
FIG. 8 is an electrochemical impedance spectrum of a bi-ionic water system energy storage device;
FIG. 9 shows a dual-ion water system energy storage device at 200mV s-1A plot of cycling stability at scan rate;
fig. 10 is a Ragone diagram of a bi-ionic water-based energy storage device.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. The embodiments of the invention will be further described with reference to the accompanying drawings and specific implementation thereof:
(1) the specific process for preparing the CuO nano array electrode based on the anode material is as follows:
a. ultrasonically cleaning a commercial metal copper sheet in deionized water, an acid solution and ethanol for 20min in sequence, and vacuum-drying for 12h at 80 ℃;
b. preparing 6M KOH electrolyte, using a direct current stable power supply, preparing Cu (OH) by an anodic oxidation method at the voltage of 1V for 20min2An electrode;
c. in thatAnd (3) under the argon atmosphere, firstly preserving heat for 3h at 150 ℃ and then preserving heat for 3h at 200 ℃ through high temperature. Mixing Cu (OH)2And (5) dehydrating to prepare the CuO nanowire.
(2) Based on cathode material VC/V2O3The specific process for preparing the/C nano composite electrode is as follows:
a. ultrasonically cleaning commercial carbon cloth in deionized water, acid solution and ethanol for 20min in sequence, and vacuum-drying at 80 ℃ for 12 h;
b. VOSO with 1M configuration4The electrolyte is used for depositing vanadium oxide on the commercial carbon cloth by an electrochemical deposition technology, wherein the voltage is 1.5V, and the time is 2 min;
c. putting the vanadium oxide deposited on the carbon cloth into 1.5M glucose aqueous solution, and soaking for 8 hours;
d. and (3) carbonizing the surface of the vanadium oxide into vanadium carbide by sintering at the high temperature of 1200 ℃ for 90min under the argon atmosphere.
CuO nano array electrode as anode, VC/V2O3the/C nano composite electrode is used as a negative electrode and assembled into a bi-ionic water system energy storage device, and the electrochemical test method comprises the following steps: separating the positive electrode material and the negative electrode material by using a diaphragm, immersing the positive electrode material and the negative electrode material into 2M KOH electrolyte, wherein the voltage windows of a cyclic voltammetry curve and a charge-discharge curve are 0-1.2V, and changing the scanning rate to obtain cyclic voltammetry curves at different scanning rates, as shown in FIG. 5; calculating the area specific capacities at different scan rates, as shown in fig. 6; changing the current density to obtain a charge-discharge curve under different current densities, as shown in fig. 7; performing electrochemical impedance spectroscopy, as shown in fig. 8; at 200mV s-1Calculating the capacity retention rate of the initial curve by 10000 cycles at the scanning rate, as shown in fig. 9; the electrochemical energy density and power density are plotted as shown in fig. 10.
CuO nano array electrode as anode material and VC/V as cathode material2O3the/C nanocomposite electrode was characterized as follows:
the surface morphology of the sample was characterized by Scanning Electron Microscopy (SEM). As shown in FIG. 1, a uniform nano array is directly grown on the surface of a metal copper sheet by an anodic oxidation method, so that the specific surface area of the material is effectively improved. As shown in fig. 2a, a layer of vanadium oxide with uniform size is coated on the surface of the carbon cloth by an electrochemical deposition technology; as shown in fig. 2b, on the basis of electrodeposition, vanadium oxide on the surface of the carbon cloth is coated by a layer of denser vanadium carbide through carbon coating and high-temperature sintering.
The surface morphology of the sample was characterized by XRD spectrogram. As shown in fig. 3, CuO was grown on commercial metal copper sheets after anodization. As shown in FIG. 4, it can be seen from FIG. 4a that V was successfully produced after electrochemical deposition2O3a/C electrode; as can be seen from FIG. 4b, VC/V was successfully prepared after carbon coating and high-temperature sintering2O3a/C nano composite electrode.
Electrochemical testing was as follows:
in the dual-ion water system energy storage device, the scanning speed is from 5 to 200mV s-1Obtaining cyclic voltammetry curves at various rates, wherein the device has redox peaks in the cyclic voltammetry curves at different scanning rates, and shows good dual-ion energy storage characteristics, as shown in fig. 5; at 5mV s-1When the area specific capacity of the device is up to 124.97mF cm-2As shown in fig. 6; the current density is from 1 to 5mA cm-2Obtaining cyclic voltammetry curves at various rates, wherein the charge-discharge curves of the device keep good symmetry along with the increase of current density, and show good rate performance, as shown in fig. 7; through electrochemical impedance spectrum test, the solution resistance R of the device can be foundIOnly 1.25ohms, charge transfer resistance RctIs 1.39ohms and the slope is nearly perpendicular to the real part in the low frequency region, indicating that the device exhibits electrochemical performance close to that of an ideal energy storage device, as shown in fig. 8.
As shown in FIG. 9, the voltage window is 0-1.2V, and the scan rate is 200mV s-1The bi-ionic water system energy storage device is tested by cyclic voltammetry, and after 10000 times of cyclic voltammetry tests, the capacity retention rate is 86.78%, and excellent cyclic stability is shown.
As shown in FIG. 10, at 0.75mW cm-2The energy density of the prepared dual-ion water system energy storage device is as high as 24.99 mu Wh cm-2The energy storage device prepared by the invention has higher energy density and has a very good application prospect in the energy storage device.
Claims (2)
1. A preparation method of a bi-ionic water system energy storage device is characterized by comprising the following steps:
through a cathode material CuO nano array electrode and an anode material VC/V2O3The energy storage device assembled by the/C nano composite electrode can simultaneously store K in a water system environment+And OH-So that it obtains a higher energy density:
the preparation method of the cathode material CuO nano array electrode comprises the following steps:
a. ultrasonic cleaning a metal substrate in deionized water, an acid solution and ethanol in sequence, and vacuum drying;
b. preparing KOH electrolyte with certain concentration, and preparing a metal hydroxide electrode by a direct-current stable power supply anodic oxidation method;
c. dehydrating the metal hydroxide by high-temperature sintering under the argon atmosphere to obtain a metal oxide nanowire;
the metal substrate in the step a is a commercial metal copper sheet, the ultrasonic cleaning time is 10-30 min, the vacuum drying temperature is 40-100 ℃, and the drying time is 6-12 h;
the concentration of KOH in the step b is 2-6M, the anodic oxidation voltage is 1-3V, the time is 20-60 min, the anode in the electrolytic cell is a copper sheet, the cathode is a platinum sheet, and the metal hydroxide is Cu (OH)2The metal oxide is CuO;
the high temperature condition in the step c is that the temperature is firstly preserved for 3h at 150 ℃, and then preserved for 3h at 200-350 ℃;
the negative electrode material VC/V2O3The preparation steps of the/C nano composite electrode are as follows:
a. ultrasonically cleaning commercial carbon cloth in deionized water, acid solution and ethanol in sequence, and drying in vacuum;
b. preparing VOSO with certain concentration4An electrolyte, which is used for depositing vanadium oxide on the commercial carbon cloth through an electrochemical deposition technology;
c. soaking the vanadium oxide deposited on the carbon cloth in a glucose aqueous solution with a certain concentration for several hours;
d. carbonizing the surface of the vanadium oxide into vanadium carbide by high-temperature sintering in an argon atmosphere;
in the step a, ultrasonic cleaning is carried out for 10-30 min, the vacuum drying temperature is 40-100 ℃, and the drying time is 6-12 h;
in the step b, in a three-electrode system, the working electrode is carbon cloth, the counter electrode is a platinum sheet, and the reference electrode is Ag/AgCl; VOSO4The concentration is 0.5-2M, the electrochemical deposition voltage is 1-3V, and the time is 1-5 min;
the concentration of the glucose aqueous solution in the step c is 1-3M, and the soaking time is 6-12 h;
and d, the high-temperature sintering temperature in the step d is 900-1200 ℃, and the time is 60-120 min.
2. The method of claim 1, wherein the selective storage of OH is performed in a bi-ionic aqueous energy storage device-The positive electrode material of (3) may include CuO, NiO and Co3O4A mixture of one or more of them.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106229563A (en) * | 2016-10-02 | 2016-12-14 | 复旦大学 | A kind of flexible aquo-lithium ion battery with self-healing function and preparation method thereof |
WO2019184939A1 (en) * | 2018-03-28 | 2019-10-03 | 华南师范大学 | Electrochemical- and photoelectrochemical-based ion removal device, preparation method thereof and application thereof |
-
2020
- 2020-10-01 CN CN202011064878.3A patent/CN112382513B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106229563A (en) * | 2016-10-02 | 2016-12-14 | 复旦大学 | A kind of flexible aquo-lithium ion battery with self-healing function and preparation method thereof |
WO2019184939A1 (en) * | 2018-03-28 | 2019-10-03 | 华南师范大学 | Electrochemical- and photoelectrochemical-based ion removal device, preparation method thereof and application thereof |
Non-Patent Citations (3)
Title |
---|
双离子电池的研究与应用;杨景海等;《吉林师范大学学报(自然科学版)》;20200510(第02期);全文 * |
基于阵列电极的新型混合电容器;刘文燚等;《物理化学学报》;20191011(第02期);全文 * |
钾离子电池中碳负极材料的研究进展;雷宇等;《新型炭材料》;20191215(第06期);全文 * |
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