CN108831757A - A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge - Google Patents
A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention discloses a kind of preparation methods of N and S codope graphene/carbon nano-tube aeroge, belong to electrode material preparation technical field.After first mixing carboxylic acid carbon nano tube and graphene oxide, deionized water is added, obtains mixed liquor after ultrasound is uniform；Pyrroles and thiophene are added into mixed liquor, carries out a hydro-thermal reaction, obtains hydrogel；Obtained hydrogel is put into the KNO of 2M3In solution, secondary hydro-thermal reaction is carried out, after being cooled to room temperature, using filter, washing and freeze-drying；Products therefrom thermal cracking in argon atmosphere after being freeze-dried, is made N the and S codope graphene/carbon nano-tube aeroge.Present invention N and S in graphene aerogel, wherein the codope of N and S can further enhance the reactivity and electric conductivity of carbon material, compared to single N or S dopant material, by introducing more active sites, to improve its chemical property, it is expected in the electrode material applied to supercapacitor.
Description
Technical field
The invention belongs to electrode material preparation technical fields, and in particular to a kind of N and S codope graphene/carbon nano-tube
The preparation method of aeroge.
Background technique
In all carbon materials, as carbon nanotube, nanofiber, porous carbon, hollow nano-sphere, carbon paste capsule, graphene are received
Rice piece, graphene nanobelt and its composite material, graphene are better than other carbon materials due to its outstanding electronics and mechanical performance
Material.Although graphene has been achieved for sizable progress in supercapacitor, performance is still barely satisfactory.This is because
Strong Van der Waals force and the interaction of π-π lamination between graphene layer form graphite-like structure so that they are easy aggregation, thus
The loss for leading to effective ratio area reduces its specific capacitance.Therefore, in order to make full use of the chemical property of graphene, it is necessary to
Effectively inhibit it from stack-up issue.
Graphene aerogel represents a kind of novel globality carbonaceous material, flourishing hole, ultralow density with
And excellent conductive characteristic imparts graphene aerogel before the wide application in the fields such as the energy, environmental protection and catalysis
Scape is research hotspot in recent years.
Summary of the invention
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of N and S codope graphene/carbon nano-tube gas
The preparation method of gel.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge, specifically includes following steps：
（1）The preparation of carboxylic acid carbon nano tube；
（2）The preparation of graphene oxide；
（3）By step（1）Carboxylic acid carbon nano tube obtained and step（2）After graphene oxide obtained mixing, addition go from
Sub- water obtains the mixed liquor that concentration is 2mg/mL after ultrasound is uniform；
（4）Toward step（3）Pyrroles and thiophene are added in obtained mixed liquor, carries out a hydro-thermal reaction, reaction temperature is 160 ~
180 DEG C, the reaction time is 4 ~ 6h, obtains hydrogel；
（5）By step（4）Obtained hydrogel is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature 120 are carried out
~ 140 DEG C, the reaction time is 2 ~ 3h, after being cooled to room temperature, using filter, washing and freeze-drying；
（6）By step（5）Institute is made in products therefrom thermal cracking 2h at 1050 ~ 1100 DEG C in argon atmosphere after freeze-drying
State N and S codope graphene/carbon nano-tube aeroge.
Step（1）The preparation method of the carboxylic acid carbon nano tube is：By 1 g multi-walled carbon nanotube（MWCNTs）Add
Enter to the dense HNO of 80 mL3In, 12 h then are condensed back in 120 DEG C of oil bath pans, gained black mixture is washed into pumping repeatedly
Filter to pH=7 take filter residue.
Step（2）The preparation method of the graphene oxide is：Graphite is uniformly mixed with the concentrated sulfuric acid/concentrated phosphoric acid system
Afterwards, it is slowly added to potassium permanganate, after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and protect
Temperature is held lower than 100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution, reaction 5 is added
After minute, it is washed with deionized to neutrality, and use BaCl2Detect the presence of SO4 2-Residual, then oxidation is made in freeze-drying for 24 hours
Powdered graphite；Graphite oxide powder obtained is add to deionized water, ultrasonic 1h, then under the revolving speed of 2000r/min
Be centrifuged 10min, remove lower sediment thing, take upper liquid, after upper liquid is freezed 12h at 0 DEG C, be placed in freeze drier into
Row freeze-drying 36h, obtains the graphene oxide.
In the concentrated sulfuric acid/concentrated phosphoric acid system, the volume ratio of the concentrated sulfuric acid and concentrated phosphoric acid is 9:1.
Step（3）The mass ratio of the carboxylic acid carbon nano tube and graphene oxide is 1:1.
Step（4）Described in pyrroles and thiophene mass ratio be 1:1, wherein the additional amount of pyrroles is graphene oxide
1wt%。
N and S codope graphene/carbon nano-tube aeroge obtained is used in electrode material, the specific steps are：By N
With S codope graphene/carbon nano-tube aeroge, acetylene black, ptfe emulsion according to mass ratio be 90:5:5 ratio
It is added in same weighing bottle, is uniformly mixed and sample is blown to paste with hair dryer, using nickel foam as collector, by paste
Material is coated in nickel foam, is dried in vacuo at 120 DEG C for 24 hours, final that required electrode is made.
The beneficial effects of the present invention are：
（1）The present invention is inserted into carbon nanotube between graphene synusia, helps to improve the electric conductivity of graphene layer, and carbon is received
Mitron can be used as spacer also to prevent the aggregation of graphene layer；In addition, low-dimensional carbon material is self-assembled into three-dimensional porous nano knot
Network forming network can greatly improve its specific surface area, and big electrode/electrolyte contact area is provided for charge transfer reaction, shorten
Ion transport length, to improve chemical property；
（2）Present invention N and S in graphene aerogel, wherein the codope of N and S can further enhance the reaction of carbon material
Property and electric conductivity, compared to single N or S dopant material, by introducing more active sites, to improve its electrochemistry
Energy.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge, specifically includes following steps：
（1）The preparation of carboxylic acid carbon nano tube：By 1 g multi-walled carbon nanotube（MWCNTs）It is added to the dense HNO of 80 mL3In, with
12 h are condensed back in 120 DEG C of oil bath pans afterwards, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter residue；
（2）The preparation of graphene oxide：By graphite and the concentrated sulfuric acid/concentrated phosphoric acid system（v/v=9:1）After evenly mixing, it is slowly added to
Potassium permanganate after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and temperature is kept to be lower than
100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reaction after five minutes, is spent
Ion water washing uses BaCl to neutrality2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours；It will
Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged 10min under the revolving speed of 2000r/min, goes
Except lower sediment thing, upper liquid is taken, after upper liquid is freezed 12h at 0 DEG C, is placed in freeze drier and is freeze-dried
36h obtains the graphene oxide；
（3）Take 50mg step（1）Carboxylic acid carbon nano tube obtained and 50mg step（2）After graphene oxide mixing obtained,
50mL deionized water is added, the mixed liquor that concentration is 2mg/mL is obtained after ultrasound is uniform；
（4）Toward step（3）The pyrroles of 0.5mg and the thiophene of 0.5mg are added in obtained mixed liquor, carries out a hydro-thermal reaction,
Reaction temperature is 160 DEG C, and reaction time 6h obtains hydrogel；
（5）By step（4）Obtained hydrogel is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature 120 are carried out
DEG C, reaction time 3h, after being cooled to room temperature, using filter, washing and freeze-drying；
（6）By step（5）Products therefrom thermal cracking 2h at 1050 DEG C in argon atmosphere, is made the N and S after freeze-drying
Codope graphene/carbon nano-tube aeroge.
Embodiment 2
A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge, specifically includes following steps：
（1）The preparation of carboxylic acid carbon nano tube：By 1 g multi-walled carbon nanotube（MWCNTs）It is added to the dense HNO of 80 mL3In, with
12 h are condensed back in 120 DEG C of oil bath pans afterwards, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter residue；
（2）The preparation of graphene oxide：By graphite and the concentrated sulfuric acid/concentrated phosphoric acid system（v/v=9:1）After evenly mixing, it is slowly added to
Potassium permanganate after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and temperature is kept to be lower than
100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reaction after five minutes, is spent
Ion water washing uses BaCl to neutrality2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours；It will
Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged 10min under the revolving speed of 2000r/min, goes
Except lower sediment thing, upper liquid is taken, after upper liquid is freezed 12h at 0 DEG C, is placed in freeze drier and is freeze-dried
36h obtains the graphene oxide；
（3）Take 50mg step（1）Carboxylic acid carbon nano tube obtained and 50mg step（2）After graphene oxide mixing obtained,
50mL deionized water is added, the mixed liquor that concentration is 2mg/mL is obtained after ultrasound is uniform；
（4）Toward step（3）The pyrroles of 0.5mg and the thiophene of 0.5mg are added in obtained mixed liquor, carries out a hydro-thermal reaction,
Reaction temperature is 180 DEG C, and reaction time 4h obtains hydrogel；
（5）By step（4）Obtained hydrogel is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature 140 are carried out
DEG C, reaction time 2h, after being cooled to room temperature, using filter, washing and freeze-drying；
（6）By step（5）Products therefrom thermal cracking 2h at 1100 DEG C in argon atmosphere, is made the N and S after freeze-drying
Codope graphene/carbon nano-tube aeroge.
Embodiment 3
A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge, specifically includes following steps：
（1）The preparation of carboxylic acid carbon nano tube：By 1 g multi-walled carbon nanotube（MWCNTs）It is added to the dense HNO of 80 mL3In, with
12 h are condensed back in 120 DEG C of oil bath pans afterwards, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter residue；
（2）The preparation of graphene oxide：By graphite and the concentrated sulfuric acid/concentrated phosphoric acid system（v/v=9:1）After evenly mixing, it is slowly added to
Potassium permanganate after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and temperature is kept to be lower than
100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reaction after five minutes, is spent
Ion water washing uses BaCl to neutrality2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours；It will
Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged 10min under the revolving speed of 2000r/min, goes
Except lower sediment thing, upper liquid is taken, after upper liquid is freezed 12h at 0 DEG C, is placed in freeze drier and is freeze-dried
36h obtains the graphene oxide；
（3）Take 50mg step（1）Carboxylic acid carbon nano tube obtained and 50mg step（2）After graphene oxide mixing obtained,
50mL deionized water is added, the mixed liquor that concentration is 2mg/mL is obtained after ultrasound is uniform；
（4）Toward step（3）The pyrroles of 0.5mg and the thiophene of 0.5mg are added in obtained mixed liquor, carries out a hydro-thermal reaction,
Reaction temperature is 170 DEG C, and reaction time 5h obtains hydrogel；
（5）By step（4）Obtained hydrogel is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature 130 are carried out
DEG C, reaction time 2.5h, after being cooled to room temperature, using filter, washing and freeze-drying；
（6）By step（5）Products therefrom thermal cracking 2h at 1080 DEG C in argon atmosphere, is made the N and S after freeze-drying
Codope graphene/carbon nano-tube aeroge.
Comparative example 1
A kind of preparation method of N doped graphene/carbon nanotube aerogel, specifically includes following steps：
（1）The preparation of carboxylic acid carbon nano tube：By 1 g multi-walled carbon nanotube（MWCNTs）It is added to the dense HNO of 80 mL3In, with
12 h are condensed back in 120 DEG C of oil bath pans afterwards, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter residue；
（2）The preparation of graphene oxide：By graphite and the concentrated sulfuric acid/concentrated phosphoric acid system（v/v=9:1）After evenly mixing, it is slowly added to
Potassium permanganate after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and temperature is kept to be lower than
100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reaction after five minutes, is spent
Ion water washing uses BaCl to neutrality2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours；It will
Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged 10min under the revolving speed of 2000r/min, goes
Except lower sediment thing, upper liquid is taken, after upper liquid is freezed 12h at 0 DEG C, is placed in freeze drier and is freeze-dried
36h obtains the graphene oxide；
（3）Take 50mg step（1）Carboxylic acid carbon nano tube obtained and 50mg step（2）After graphene oxide mixing obtained,
50mL deionized water is added, the mixed liquor that concentration is 2mg/mL is obtained after ultrasound is uniform；
（4）Toward step（3）The pyrroles of 1mg is added in obtained mixed liquor, carries out a hydro-thermal reaction, reaction temperature is 170 DEG C,
Reaction time is 5h, obtains hydrogel；
（5）By step（4）Obtained hydrogel is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature 130 are carried out
DEG C, reaction time 2.5h, after being cooled to room temperature, using filter, washing and freeze-drying；
（6）By step（5）Products therefrom thermal cracking 2h at 1080 DEG C in argon atmosphere, is made the N and mixes after freeze-drying
Miscellaneous graphene/carbon nano-tube aeroge.
Comparative example 2
A kind of preparation method of S doped graphene/carbon nanotube aerogel, specifically includes following steps：
（1）The preparation of carboxylic acid carbon nano tube：By 1 g multi-walled carbon nanotube（MWCNTs）It is added to the dense HNO of 80 mL3In, with
12 h are condensed back in 120 DEG C of oil bath pans afterwards, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter residue；
（2）The preparation of graphene oxide：By graphite and the concentrated sulfuric acid/concentrated phosphoric acid system（v/v=9:1）After evenly mixing, it is slowly added to
Potassium permanganate after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and temperature is kept to be lower than
100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reaction after five minutes, is spent
Ion water washing uses BaCl to neutrality2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours；It will
Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged 10min under the revolving speed of 2000r/min, goes
Except lower sediment thing, upper liquid is taken, after upper liquid is freezed 12h at 0 DEG C, is placed in freeze drier and is freeze-dried
36h obtains the graphene oxide；
（3）Take 50mg step（1）Carboxylic acid carbon nano tube obtained and 50mg step（2）After graphene oxide mixing obtained,
50mL deionized water is added, the mixed liquor that concentration is 2mg/mL is obtained after ultrasound is uniform；
（4）Toward step（3）The thiophene of 0.1mg is added in obtained mixed liquor, carries out a hydro-thermal reaction, reaction temperature 170
DEG C, reaction time 5h obtains hydrogel；
（5）By step（4）Obtained hydrogel is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature 130 are carried out
DEG C, reaction time 2.5h, after being cooled to room temperature, using filter, washing and freeze-drying；
（6）By step（5）Products therefrom thermal cracking 2h at 1080 DEG C in argon atmosphere, is made the S and mixes after freeze-drying
Miscellaneous graphene/carbon nano-tube aeroge.
By N and S codope graphene/carbon nano-tube aeroge obtained above, N doped graphene/carbon nanotube airsetting
Glue and S doped graphene/carbon nanotube aerogel are used in electrode material, the specific steps are：By N and S codope graphene/carbon
Nanotube aeroge（Or N doped graphene/carbon nanotube aerogel, S doped graphene/carbon nanotube aerogel）, acetylene black,
Ptfe emulsion is 90 according to mass ratio:5:5 ratio is added in same weighing bottle, is uniformly mixed and uses hair dryer
Sample is blown to paste, using nickel foam as collector, pastes is coated in nickel foam, is dried in vacuo at 120 DEG C
For 24 hours, final that required electrode is made.
Electrode obtained is subjected to density, specific surface area and electrochemical property test, the results are shown in Table 1.
The properties of 1 silica aerogel electrode of table
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with repair
Decorations, are all covered by the present invention.
Claims (7)
1. a kind of preparation method of N and S codope graphene/carbon nano-tube aeroge, it is characterised in that：Specifically include following step
Suddenly：
（1）The preparation of carboxylic acid carbon nano tube；
（2）The preparation of graphene oxide；
（3）By step（1）Carboxylic acid carbon nano tube obtained and step（2）After graphene oxide obtained mixing, addition go from
Sub- water obtains the mixed liquor that concentration is 2mg/mL after ultrasound is uniform；
（4）Toward step（3）Pyrroles and thiophene are added in obtained mixed liquor, carries out a hydro-thermal reaction, reaction temperature is 160 ~
180 DEG C, the reaction time is 4 ~ 6h, obtains hydrogel；
（5）By step（4）Obtained hydrogel is put into the KNO of 2M3In solution, secondary hydro-thermal reaction is carried out, reaction temperature is 120 ~
140 DEG C, the reaction time is 2 ~ 3h, after being cooled to room temperature, using filter, washing and freeze-drying；
（6）By step（5）Institute is made in products therefrom thermal cracking 2h at 1050 ~ 1100 DEG C in argon atmosphere after freeze-drying
State N and S codope graphene/carbon nano-tube aeroge.
2. the preparation method of N and S codope graphene/carbon nano-tube aeroge according to claim 1, feature exist
In：Step（1）The preparation method of the carboxylic acid carbon nano tube is：It is dense that 1 g multi-walled carbon nanotube is added to 80 mL
HNO3In, 12 h then are condensed back in 120 DEG C of oil bath pans, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter
Slag.
3. the preparation method of N and S codope graphene/carbon nano-tube aeroge according to claim 1, feature exist
In：Step（2）The preparation method of the graphene oxide is：After evenly mixing by graphite and the concentrated sulfuric acid/concentrated phosphoric acid system, delay
It is slow to be added potassium permanganate, after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, it is slowly added to deionized water, and keep temperature
Lower than 100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reacts after five minutes,
It is washed with deionized to neutrality, and uses BaCl2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours
End；Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged under the revolving speed of 2000r/min
10min, remove lower sediment thing, take upper liquid, after upper liquid is freezed 12h at 0 DEG C, be placed in freeze drier carry out it is cold
Dry 36h is lyophilized, obtains the graphene oxide.
4. the preparation method of N and S codope graphene/carbon nano-tube aeroge according to claim 3, feature exist
In：In the concentrated sulfuric acid/concentrated phosphoric acid system, the volume ratio of the concentrated sulfuric acid and concentrated phosphoric acid is 9:1.
5. the preparation method of N and S codope graphene/carbon nano-tube aeroge according to claim 1, feature exist
In：Step（3）The mass ratio of the carboxylic acid carbon nano tube and graphene oxide is 1:1.
6. the preparation method of N and S codope graphene/carbon nano-tube aeroge according to claim 1, feature exist
In：Step（4）Described in pyrroles and thiophene mass ratio be 1:1, wherein the additional amount of pyrroles is the 1wt% of graphene oxide.
7. N and S codope graphene/carbon nano-tube aeroge is in electricity made from a kind of preparation method as described in claim 1
Application in the material of pole, it is characterised in that：By N and S codope graphene/carbon nano-tube aeroge, acetylene black, polytetrafluoroethylene (PTFE)
Lotion is 90 according to mass ratio:5:5 ratio is added in same weighing bottle, is uniformly mixed and is blown to sample with hair dryer
Pastes is coated in nickel foam by paste using nickel foam as collector, is dried in vacuo at 120 DEG C for 24 hours, final to be made
Required electrode.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110127665A (en) * | 2019-05-18 | 2019-08-16 | 黑龙江八一农垦大学 | Multi-walled carbon nanotube/graphene aerogel and its method for detecting organophosphorus pesticide |
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| CN110127665A (en) * | 2019-05-18 | 2019-08-16 | 黑龙江八一农垦大学 | Multi-walled carbon nanotube/graphene aerogel and its method for detecting organophosphorus pesticide |
| CN110316720A (en) * | 2019-06-27 | 2019-10-11 | 沈健民 | Sulphur, nitrogen codope carbon nano-tube film and preparation method thereof |
| CN114220670A (en) * | 2021-12-16 | 2022-03-22 | 福州大学 | Preparation method of non-covalent hybrid MOF graphene aerogel/molybdenum capacitor electrode material |
| CN114220670B (en) * | 2021-12-16 | 2023-09-12 | 福州大学 | Preparation method of non-covalent hybridized MOF graphene aerogel/molybdenum capacitor electrode material |
| CN115472440A (en) * | 2022-08-18 | 2022-12-13 | 兰州大学 | Graphene-based N, S doped electrode material and preparation method thereof |
| CN115472440B (en) * | 2022-08-18 | 2024-03-15 | 兰州大学 | Graphene-based N, S doped electrode material and preparation method thereof |
| CN115536009A (en) * | 2022-10-14 | 2022-12-30 | 安徽科技学院 | Preparation method of nitrogen and sulfur co-doped graphene multi-walled carbon nanotube composite membrane |
| CN115536009B (en) * | 2022-10-14 | 2023-08-08 | 安徽科技学院 | Preparation method of nitrogen-sulfur co-doped graphene multiwall carbon nanotube composite film |
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