CN108264135A - Capacitive desalination electrode and preparation method thereof - Google Patents
Capacitive desalination electrode and preparation method thereof Download PDFInfo
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- 238000010612 desalination reaction Methods 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 121
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 229910021389 graphene Inorganic materials 0.000 claims description 41
- 229910014235 MyOz Inorganic materials 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000007795 chemical reaction product Substances 0.000 claims description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- 206010013786 Dry skin Diseases 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 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 10
- 239000008103 glucose Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 5
- -1 alkene compound Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002527 Glycogen Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 229940096919 glycogen Drugs 0.000 claims description 3
- 229920001542 oligosaccharide Polymers 0.000 claims description 3
- 150000002482 oligosaccharides Chemical class 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000011734 sodium Substances 0.000 abstract description 102
- 238000011033 desalting Methods 0.000 abstract description 39
- 239000000463 material Substances 0.000 abstract description 17
- 241000370738 Chlorion Species 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 10
- 238000009831 deintercalation Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 abstract description 8
- 229960003351 prussian blue Drugs 0.000 abstract description 8
- 239000013225 prussian blue Substances 0.000 abstract description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 229940073609 bismuth oxychloride Drugs 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 41
- 239000011780 sodium chloride Substances 0.000 description 21
- 230000007423 decrease Effects 0.000 description 6
- 238000002242 deionisation method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- GLQBXSIPUULYOG-UHFFFAOYSA-M bismuth oxychloride Chemical group Cl[Bi]=O GLQBXSIPUULYOG-UHFFFAOYSA-M 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Electrochemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Capacitive desalination electrode provided by the invention and preparation method thereof, utilizes sodium titanate (NaxTiyOz), sodium manganate (NaxMnyOz), cobalt acid sodium (NaxCoyOz) and its compound as embedded capacitance desalination cathode, the material that can be reacted with chlorion is anode (such as carbon, Prussian blue, silver-colored and bismuth oxychloride material), form double ion deintercalation electrode, in respective electrode so as to which sodium ion in bitter alkali water/haline water and chlorion are embedded in chemical bond form, achieve the purpose that efficient desalination.Compared with Electrostatic Absorption capacitive desalination method, since ion is removed in a manner of bonding, so desalting efficiency and charge efficiency can be substantially improved and some negative effects present in Electrostatic Absorption capacitive desalination can obtain good inhibition, such as electric double layer screen effect and common-ion effect.
Description
Technical field
The present invention relates to bitter alkali water desalting technology fields more particularly to a kind of capacitive desalination electrode and preparation method thereof.
Background technology
Capacitive desalination (also known as capacitive deionization), is a kind of technique for desalting salt water based on electric double layer capacitance model, base
Present principles are to force to move at the electrode with opposite charges by the anions and canons in bitter alkali water by applying electrode electrostatic field
It moves and is adsorbed in electrode surface and form electric double layer, so as to reach desalination or go deionization purpose.Capacitive desalination electricity common at present
Pole material is mainly made of inertia height, large specific surface area and the carbon being readily mass-produced and its composite material, including：Active powdered carbon
End, carbon aerogels, carbon nanotube, graphene etc..However there are hole knots for the symmetrical capacitive deionization method of use carbon-based electrode
The shortcomings such as structure is complicated, effective surface area is low, electric double layer eclipsing effects, desalting efficiency difference are low with charge efficiency, Electrostatic Absorption mode
Attainable salt rejection rate<20mg/g, and charge efficiency is usually 60% or so.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of capacitive desalination electrode and preparation method thereof, NaxMyOz(M=
Ti, Mn, Co) or NaxMyOz(M=Ti, Mn, Co) compound is arranged as capacitive desalination negative electrode using asymmetric electrode
Salt ion is embedded in the electrodes, so as to greatly improve the desalination side of capacitive desalination efficiency by mode, the mode for introducing chemical bonding
Method.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of capacitive desalination electrode, uses NaxMyOzAs the negative electrode of capacitive desalination, wherein M is Ti or Mn or Co.
Optimal, use Na4Ti9O20Negative electrode as capacitive desalination.
A kind of capacitive desalination electrode, uses NaxMyOzWith the negative electrode of the compound of graphene as capacitive desalination,
Middle M is Ti or Mn or Co.
Optimal, use Na4Ti9O20With the negative electrode of the compound of graphene as capacitive desalination.
A kind of preparation method of capacitive desalination electrode prepares NaxMyOzAnd the step of graphene complex, includes：
Mixing：By TiO2, NaOH and graphene oxide be stirred well to uniformly mixed, obtain mixture；
Reaction：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box, 150
Hydro-thermal reaction is carried out at~230 DEG C 0.5~24 hour, obtain reaction product；
It is dry：Reaction product is washed to neutrality, is then transferred in insulating box 50~90 DEG C of dryings at least 2 hours, i.e.,
Obtain NaxMyOzWith the compound of graphene.
A kind of preparation method of capacitive desalination electrode prepares Na4Ti9O20And the step of graphene complex, includes：
Mixing：By 0.3g TiO2, 50ml 10mol/L NaOH and 8mg graphene oxides be stirred well to it is uniformly mixed,
Obtain mixture.
Reaction：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box, 200
Hydro-thermal reaction is carried out at DEG C 4 hours, obtain reaction product；
It is dry：Reaction product is washed to neutrality, is then transferred in insulating box 50~90 DEG C of dryings at least 2 hours, i.e.,
Obtain Na4Ti9O20With the compound of graphene.
A kind of capacitive desalination electrode, uses NaxMyOzWith the negative electrode of the compound of carbon as capacitive desalination, wherein M is
Ti or Mn or Co.
Optimal, use Na4Ti9O20With the negative electrode of the compound of carbon as capacitive desalination.
A kind of preparation method of capacitive desalination electrode prepares NaxMyOzInclude with the step of compound of carbon：
Mixing：By TiO2, NaOH be stirred well to uniformly mixed, obtain mixture；
Reaction：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box, 150
Hydro-thermal reaction is carried out at~1230 DEG C 0.5~24 hour, obtain reaction product；
It is dry：Reaction product is washed to neutrality, is then transferred in insulating box 50~90 DEG C of dryings at least 2 hours, i.e.,
Obtain NaxMyOz；
Add carbon：By the Na of gainedxMyOzIt is stirred well to and is uniformly mixed with carbon source solution, obtain treating reactant, wherein described
Carbon source is at least one of sucrose, glucose, glycogen, cellulose, oligosaccharide, polysaccharide；
Secondary response：It treats that reactant is moved in the autoclave of polytetrafluoroethyllining lining by what is obtained, is put into insulating box
In, hydro-thermal reaction is carried out at 140~170 DEG C, until NaxMyOzOuter layer covers layer carbon source, obtains secondary response product；
Redrying：Gained secondary response product is washed, it is small to be then transferred to 50~90 DEG C of dryings at least 2 in insulating box
When, obtain dried object；
Heat treatment：By dried object under conditions of nitrogen protection, 300 are warming up to the heating rate of 1~10 DEG C/min~
500 DEG C, 2~6 hours then are kept the temperature at 300~500 DEG C, obtains Na after reactionxMyOzWith the compound of carbon.
A kind of preparation method of capacitive desalination electrode prepares Na4Ti9O20Include with the step of compound of carbon：
Mixing：By 0.3g TiO2, 50ml 10mol/L NaOH be stirred well to uniformly mixed, obtain mixture；
Reaction：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box, 200
Hydro-thermal reaction is carried out at DEG C 4 hours, obtain reaction product；
It is dry：Reaction product is washed to neutrality, is then transferred in insulating box 50~90 DEG C of dryings at least 2 hours, i.e.,
Obtain the Na of nano tubular structure4Ti9O20；
Add carbon：By the Na obtained by 0.15g4Ti9O20It is stirred well to and is uniformly mixed with the glucose of 25ml 0.5mol/L,
It obtains treating reactant；
Secondary response：It treats that reactant is moved in the autoclave of polytetrafluoroethyllining lining by what is obtained, is put into insulating box
In, hydro-thermal reaction is carried out at 160 DEG C 4 hours, obtain secondary response product；
Redrying：Gained secondary response product is first washed with deionized, is then washed with absolute ethyl alcohol, Zhi Houzhuan
50~90 DEG C of dryings at least 2 hours are moved in insulating box, obtain dried object；
Heat treatment：By dried object under conditions of nitrogen protection, 400 DEG C are warming up to the heating rate of 5 DEG C/min, then
4 hours are kept the temperature at 400 DEG C, obtains Na after reaction4Ti9O20With the compound of carbon.
As shown from the above technical solution, capacitive desalination electrode provided by the invention and preparation method thereof, utilizes sodium titanate
(NaxTiyOz), sodium manganate (NaxMnyOz), cobalt acid sodium (NaxCoyOz) and its compound as embedded capacitance desalination cathode, can
The material reacted with chlorion is anode (such as carbon, Prussian blue, silver-colored and bismuth oxychloride material), forms double ion deintercalation electricity
Pole in the respective electrode so as to which sodium ion in bitter alkali water/haline water and chlorion be embedded ins with chemical bond form, reaches and efficiently takes off
The purpose of salt.Compared with Electrostatic Absorption capacitive desalination method, since ion is removed in a manner of bonding, so desalting efficiency
It can be substantially improved with charge efficiency and some negative effects present in Electrostatic Absorption capacitive desalination can obtain very well
Inhibition, such as electric double layer screen effect and common-ion effect.
Description of the drawings
Attached drawing 1 is Na4Ti9O20TEM figure.
Attached drawing 2 is Na4Ti9O20In initial conductivity is 500 μ s/cm NaCl solution, under different operating voltage (0.8,
1.0,1.2,1.4V) conductivity variations situation.
Attached drawing 3 is Na4Ti9O20In initial conductivity it is different operating voltage in 500 μ s/cm NaCl solutions with activated carbon
Under (0.8,1.0,1.2,1.4V) desalting ability comparison.
Attached drawing 4 is Na4Ti9O20Scheme with the TEM of the compound of graphene.
Attached drawing 5 is Na4Ti9O20Compound with graphene is different in initial conductivity is 500 μ s/cm NaCl solution
The conductivity variations situation of (0.8,1.0,1.2,1.4V) under operating voltage.
Attached drawing 6 is Na4Ti9O20It is molten for 500 μ s/cm NaCl in initial conductivity with the compound and activated carbon of graphene
In liquid, the desalting ability comparison of (0.8,1.0,1.2,1.4V) under different operating voltage.
Attached drawing 7 is Na4Ti9O20Scheme with the HRTEM of the compound of glucose.
Attached drawing 8 is Na4Ti9O20Compound with glucose is different in initial conductivity is 500 μ s/cm NaCl solution
The conductivity variations situation of (0.8,1.0,1.2,1.4V) under operating voltage.
Attached drawing 9 is Na4Ti9O20It is molten for 500 μ s/cm NaCl in initial conductivity with the compound and activated carbon of glucose
In liquid, the desalting ability comparison of (0.8,1.0,1.2,1.4V) under different operating voltage.
Attached drawing 10 is Na4Ti9O2、Na4Ti9O20With the compound and Na of graphene4Ti9O20Compound with glucose is first
Beginning conductivity is the charge efficiency of (0.8,1.0,1.2,1.4V) under different operating voltage in 500 μ s/cmNaCl solution.
Specific embodiment
With reference to the attached drawing of the present invention, the technical solution of inventive embodiments is further elaborated.
Embodiment 1：
Use NaxMyOzAs the negative electrode of capacitive desalination, wherein M is Ti or Mn or Co.The material that can be reacted with chlorion
Expect for anode, such as the materials such as carbon, Prussian blue, silver-colored and bismuth oxychloride, composition double ion deintercalation electrode.
NaxMyOzPreparation process include the following steps：
(1) it mixes：By TiO2, NaOH be stirred well to uniformly mixed, obtain mixture.
(2) it reacts：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box,
Hydro-thermal reaction is carried out at 150~230 DEG C 0.5~4 hour, obtain reaction product.
(3) it is dry：Reaction product is washed to neutrality, is then transferred in insulating box 50~90 DEG C of dryings at least 2 hours,
Obtain NaxMyOz。
Embodiment 2：
Use Na4Ti9O20As the negative electrode of capacitive desalination, wherein M is Ti or Mn or Co.It can be reacted with chlorion
Material is anode, such as the materials such as carbon, Prussian blue, silver-colored and bismuth oxychloride, forms double ion deintercalation electrode.
Na4Ti9O20Preparation process include the following steps：
(1) it mixes：By 0.3g TiO2, 50ml 10mol/L NaOH be stirred well to it is uniformly mixed, stir 30 minutes left sides
The right side obtains mixture
(2) it reacts：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box,
Hydro-thermal reaction is carried out at 200 DEG C 4 hours, obtain reaction product.
(3) it is dry：Reaction product is washed to neutrality, i.e. pH=7, is then transferred in insulating box at 70 DEG C dry 12h,
Obtain the Na of nano tubular structure4Ti9O20。
Embodiment 3：
Use NaxMyOzWith the negative electrode of the compound of graphene as capacitive desalination, wherein M is Ti or Mn or Co.It can
The material reacted with chlorion is anode, such as materials such as carbon, Prussian blue, silver-colored and bismuth oxychloride form double ion deintercalation electricity
Pole.
NaxMyOzInclude the following steps with the preparation process of the compound of graphene：
(1) it mixes：By TiO2, NaOH and graphene oxide be stirred well to uniformly mixed, obtain mixture.
(2) it reacts：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box,
Hydro-thermal reaction is carried out at 150~230 DEG C 0.5~24 hour, obtain reaction product.
(3) it is dry：Reaction product is washed to neutrality, is then transferred in insulating box 50~90 DEG C of dryings at least 2 hours,
Obtain NaxMyOzWith the compound of graphene.
Embodiment 4：
Use Na4Ti9O20With the negative electrode of the compound of graphene as capacitive desalination, wherein M is Ti or Mn or Co.
The material that can be reacted with chlorion is anode, such as materials such as carbon, Prussian blue, silver-colored and bismuth oxychloride form double ion deintercalation
Electrode.
Na4Ti9O20Include the following steps with the preparation process of the compound of graphene：
(1) it mixes：By 0.3g TiO2, 50ml 10mol/L NaOH and 8mg graphene oxides to be stirred well to mixing equal
It is even, obtain mixture.
(2) it reacts：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box,
Hydro-thermal reaction is carried out at 200 DEG C 4 hours, obtain reaction product.
(3) it is dry：Reaction product is washed to neutrality, be then transferred in insulating box at 70 DEG C dry 12h to get to
Na4Ti9O20With the compound of graphene.
Embodiment 5：
Use NaxMyOzWith the negative electrode of the compound of carbon as capacitive desalination, wherein M is Ti or Mn or Co.It can be with chlorine
The material of ionic reaction is anode, such as materials such as carbon, Prussian blue, silver-colored and bismuth oxychloride form double ion deintercalation electrode.
NaxMyOzInclude the following steps with the preparation process of the compound of carbon：
(1) it mixes：By TiO2, NaOH be stirred well to uniformly mixed, obtain mixture.
(2) it reacts：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box,
Hydro-thermal reaction is carried out at 150~230 DEG C 0.5~24 hour, obtain reaction product.
(3) it is dry：Reaction product is washed to neutrality, is then transferred in insulating box 50~90 DEG C of dryings at least 2 hours,
Obtain NaxMyOz。
(4) add carbon：By the Na of gainedxMyOzIt is stirred well to and is uniformly mixed with carbon source solution, obtain treating reactant, wherein
The carbon source is at least one of sucrose, glucose, glycogen, cellulose, oligosaccharide, polysaccharide.
(5) secondary response：It treats that reactant is moved in the autoclave of polytetrafluoroethyllining lining by what is obtained, is put into constant temperature
In case, hydro-thermal reaction is carried out at 140~170 DEG C, until NaxMyOzOuter layer covers layer carbon source, obtains secondary response product.
(6) redrying：Gained secondary response product is washed, is then transferred in insulating box 50~90 DEG C of dryings at least
2 hours, obtain dried object.
(7) it is heat-treated：By dried object under conditions of nitrogen protection, 300 are warming up to the heating rate of 1~10 DEG C/min
~500 DEG C, 2~6 hours then are kept the temperature at 300~500 DEG C, obtains Na after reactionxMyOzWith the compound of carbon.
Embodiment 6：
Use Na4Ti9O20With the negative electrode of the compound of carbon as capacitive desalination, wherein M is Ti or Mn or Co.It can be with
The material of chlorion reaction is anode, such as the materials such as carbon, Prussian blue, silver-colored and bismuth oxychloride, forms double ion deintercalation electrode.
Na4Ti9O20Include the following steps with the preparation process of the compound of carbon：
(1) it mixes：By 0.3g TiO2, 50ml 10mol/L NaOH be stirred well to uniformly mixed, obtain mixture
(2) it reacts：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box,
Hydro-thermal reaction is carried out at 200 DEG C 4 hours, obtain reaction product.
(3) it is dry：Reaction product is washed to neutrality, is then transferred in insulating box at 70 DEG C dry 12h to get to receiving
The Na of rice tubular structure4Ti9O20。
(4) add carbon：By the Na obtained by 0.15g4Ti9O20It is stirred well to and is mixed with the glucose of 25ml 0.5mol/L
It is even, it obtains treating reactant.
(5) secondary response：It treats that reactant is moved in the autoclave of polytetrafluoroethyllining lining by what is obtained, is put into constant temperature
In case, hydro-thermal reaction is carried out at 160 DEG C 4 hours, obtain secondary response product.
(6) redrying：Gained secondary response product is first washed with deionized, is then washed with absolute ethyl alcohol, it
After be transferred in insulating box at 70 DEG C dry 12h, obtain dried object.
(7) it is heat-treated：By dried object under conditions of nitrogen protection, 400 DEG C are warming up to the heating rate of 5 DEG C/min,
Then 4 hours are kept the temperature at 400 DEG C, obtains Na after reaction4Ti9O20With the compound of carbon.
Then obtained product experimental verification, wherein Na have been subjected to4Ti9O20It is abbreviated as NTO, Na4Ti9O20And graphene
Compound is abbreviated as rGO@NTO, Na4Ti9O20C@NTO are abbreviated as with carbon complex.
The Na that will be obtained4Ti9O20, by transmission electron microscope observing, as a result as shown in Figure 1, find synthesized Na4Ti9O20
With typical nano tube structure, the internal diameter of pipe is about 5.2 rans, can be true much larger than the diameter of hydration sodium ion
The fast transfer of sodium ion is protected, and then promotes Na4Ti9O20Desalting performance.
Then in order to study Na4Ti9O20Desalting performance, we test Na4Ti9O20It is 500 μ s/ in initial conductivity
In cm NaCl solutions, under different operating voltage, i.e., 0.8, the conductivity variations feelings of NaCl solution under 1.0,1.2,1.4V voltage
Condition, as a result as shown in Figure 2, it can be seen that electrode applies operating voltage initial stage, and NaCl solution conductivity declines rapidly, shows sodium
Ion is quickly embedded in the Na as cathode4Ti9O20In, while chlorion is adsorbed on the activated carbon as anode rapidly, but with
Time passage, two electrode desalting abilities progressively reach saturation, thus conductivity decline slowly tends towards stability, and NaCl solution
Conductivity decline is bigger, and system desalting ability is better.In addition to this, we it is seen that system desalting ability with operating voltage
Increase and promoted.
Then by Na4Ti9O20As cathode, activated carbon as anode desalting ability with conventional carbon respectively as just
The desalting ability of cathode is compared, as a result as shown in Figure 3, it can be seen that Na4Ti9O20Desalting ability is substantially better than activity
Charcoal shows that embedded capacitance desalination process can promote desalting ability.Wherein desalting ability be byFormula
Calculate gained, Γ be desalting ability (mg/g), G0For initial NaCl solution concentration (mg/L), GtNaCl solution at the end of for desalination
Concentration (mg/L), V are NaCl solution total volume (L), and m is electrode gross mass (g), be set forth below desalting ability also by similary public
Formula is calculated.
The Na that will be obtained4Ti9O20As a result as shown in Figure 4 compound with graphene, is found by transmission electron microscope observing
Graphene is with reticular structure by all Na4Ti9O20Nanotube connects, and graphene serves as conducting shell, can effectively improve
Na4Ti9O20With the conductibility of graphene complex, and then its desalting performance is promoted.
In order to study Na4Ti9O20With the desalting performance of graphene complex, we test Na4Ti9O20It is answered with graphene
Object is closed in initial conductivity is 500 μ s/cm NaCl solution, under different operating voltage, i.e., 0.8,1.0,1.2,1.4V work electricity
Pressure, the conductivity variations situation of NaCl solution, as a result as shown in Figure 5, it has been found that electrode applies operating voltage initial stage,
NaCl solution conductivity declines rapidly, shows that sodium ion is quickly embedded in the Na as cathode4Ti9O20In graphene complex,
Chlorion is adsorbed in the activated carbon as anode rapidly simultaneously, but as time goes by, two electrode desalting abilities progressively reach
Saturation, thus conductivity decline slowly tends towards stability.And the decline of NaCl solution conductivity is bigger, and system desalting ability is better.
In addition to this, we are it is seen that system desalting ability is promoted as operating voltage increases.
Then by Na4Ti9O20With graphene complex as cathode, activated carbon is lived as the desalting ability of anode with tradition
Property charcoal is compared respectively as the desalting ability of positive and negative anodes, as a result as shown in Figure 6, it can be seen that Na4Ti9O20And graphene
Compound desalting ability is substantially better than activated carbon, shows Na4Ti9O20With this embedded capacitance desalination process of graphene complex
Desalting ability can be promoted.
Then by Na4Ti9O20With the compound of carbon by transmission electron microscope observing, as a result as shown in Figure 7, it is observed that
Carbon-coating is evenly coated at Na4Ti9O20Nanometer pipe outer wall, carbon layers having thicknesses are about 1.6nm.This can effectively promote Na4Ti9O20's
Electric conductivity, stability and specific surface area, so as to promote its desalting performance.
In order to study Na4Ti9O20With the desalting performance of the compound of carbon, we test Na4Ti9O20Exist with carbon complex
Initial conductivity be 500 μ s/cm NaCl solutions in, under different operating voltage, i.e., 0.8,1.0,1.2,1.4V operating voltage
Under, the conductivity variations situation of NaCl solution, as a result as shown in Figure 8, it has been found that electrode applies operating voltage initial stage, NaCl
Electrical conductivity of solution declines rapidly, shows that sodium ion is quickly embedded in the Na as cathode4Ti9O20In carbon complex, at the same chlorine from
Sub rapid absorption is in the activated carbon as anode, but as time goes by, two electrode desalting abilities progressively reach saturation, thus
Conductivity decline slowly tends towards stability.And the decline of NaCl solution conductivity is bigger, and system desalting ability is better.In addition to this,
We are it is seen that system desalting ability is promoted as operating voltage increases.
Then by Na4Ti9O20With carbon complex as cathode, desalting ability and conventional carbon of the activated carbon as anode
It is compared respectively as the desalting ability of positive and negative anodes, as a result as shown in Figure 9, we are it is seen that Na4Ti9O20It is compound with carbon
Object desalting ability is substantially better than activated carbon, shows Na4Ti9O20It can be promoted with this embedded capacitance desalination process of carbon complex
Desalting ability.
Then it compared Na4Ti9O20、Na4Ti9O20With graphene complex, Na4Ti9O20With the charge of carbon complex three
Efficiency, as a result as shown in Figure 10, Na4Ti9O20Charge efficiency is 65.58% when operating voltage is 0.8V, is being worked
Charge efficiency can reach 84.45% when voltage is 1.4V.Na4Ti9O20With graphene complex operating voltage be 0.8V
When charge efficiency be 73.64%, charge efficiency can reach 96.2% when operating voltage is 1.2V.Na4Ti9O20With
Carbon complex charge efficiency when operating voltage is 0.8V is 84.93%, and charge is imitated when operating voltage is 1.4V
Rate can reach 98.24%.The charge efficiency of currently known carbon material capacitive deionization system can be seen usually 60% or so
Go out Na4Ti9O20、Na4Ti9O20With graphene complex, Na4Ti9O20All be significantly larger than with the charge efficiency of carbon complex 60% with
On.Show that embedded capacitance desalination process can effectively promote charge utilization ratio.Wherein charge efficiency is by formulaCalculate gained, Λ be charge efficiency (%), Γ for desalting ability byFormula can be calculated
(mg/g), F is Faraday constant, and Σ is current density (A/g).
Claims (10)
1. a kind of capacitive desalination electrode, it is characterised in that：Use NaxMyOzAs the negative electrode of capacitive desalination, wherein M is Ti
Or Mn or Co.
2. capacitive desalination electrode according to claim 1, it is characterised in that：Use Na4Ti9O20As the negative of capacitive desalination
Pole electrode.
3. a kind of capacitive desalination electrode, it is characterised in that：Use NaxMyOzCompound with graphene is as the negative of capacitive desalination
Pole electrode, wherein M are Ti or Mn or Co.
4. capacitive desalination electrode according to claim 3, it is characterised in that：Use Na4Ti9O20With the compound of graphene
Negative electrode as capacitive desalination.
5. a kind of preparation method of capacitive desalination electrode, which is characterized in that prepare the Na described in claim 3xMyOzAnd graphene
The step of compound, includes：
Mixing：By TiO2, NaOH and graphene oxide be stirred well to uniformly mixed, obtain mixture；
Reaction：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box, 150~230
Hydro-thermal reaction is carried out at DEG C 0.5~24 hour, obtain reaction product；
It is dry：Reaction product is washed to neutrality, be then transferred in insulating box 50~90 DEG C of dryings at least 2 hours to get to
NaxMyOzWith the compound of graphene.
6. a kind of preparation method of capacitive desalination electrode, which is characterized in that prepare the Na described in claim 44Ti9O20And graphite
The step of alkene compound, includes：
Mixing：By 0.3g TiO2, 50ml 10mol/L NaOH and 8mg graphene oxides be stirred well to uniformly mixed, obtain
Mixture；
Reaction：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box, at 200 DEG C
It carries out hydro-thermal reaction 4 hours, obtains reaction product；
It is dry：Reaction product is washed to neutrality, be then transferred in insulating box 50~90 DEG C of dryings at least 2 hours to get to
Na4Ti9O20With the compound of graphene.
7. a kind of capacitive desalination electrode, it is characterised in that：Use NaxMyOzWith the negative electricity of the compound of carbon as capacitive desalination
Pole, wherein M are Ti or Mn or Co.
8. capacitive desalination electrode according to claim 7, it is characterised in that：Use Na4Ti9O20With the compound conduct of carbon
The negative electrode of capacitive desalination.
9. a kind of preparation method of capacitive desalination electrode, which is characterized in that prepare the Na described in claim 7xMyOzWith answering for carbon
The step of closing object includes：
Mixing：By TiO2, NaOH be stirred well to uniformly mixed, obtain mixture；
Reaction：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box, 150~230
Hydro-thermal reaction is carried out at DEG C 0.5~24 hour, obtain reaction product；
It is dry：Reaction product is washed to neutrality, be then transferred in insulating box 50~90 DEG C of dryings at least 2 hours to get to
NaxMyOz；
Add carbon：By the Na of gainedxMyOzIt is stirred well to and is uniformly mixed with carbon source solution, obtain treating reactant, wherein the carbon source
For at least one of sucrose, glucose, glycogen, cellulose, oligosaccharide, polysaccharide；
Secondary response：It treats that reactant is moved in the autoclave of polytetrafluoroethyllining lining by what is obtained, is put into insulating box,
Hydro-thermal reaction is carried out at 140~170 DEG C, until NaxMyOzOuter layer covers layer carbon source, obtains secondary response product；
Redrying：Gained secondary response product is washed, is then transferred in insulating box 50~90 DEG C of dryings at least 2 hours,
Obtain dried object；
Heat treatment：By dried object under conditions of nitrogen protection, 300~500 are warming up to the heating rate of 1~10 DEG C/min
DEG C, 2~6 hours then are kept the temperature at 300~500 DEG C, obtains Na after reactionxMyOzWith the compound of carbon.
10. a kind of preparation method of capacitive desalination electrode, which is characterized in that prepare Na according to any one of claims 84Ti9O20With carbon
The step of compound, includes：
Mixing：By 0.3g TiO2, 50ml 10mol/L NaOH be stirred well to uniformly mixed, obtain mixture；
Reaction：Gained mixture is moved in the autoclave of polytetrafluoroethyllining lining, be put into insulating box, at 200 DEG C
It carries out hydro-thermal reaction 4 hours, obtains reaction product；
It is dry：Reaction product is washed to neutrality, be then transferred in insulating box 50~90 DEG C of dryings at least 2 hours to get to
The Na of nano tubular structure4Ti9O20；
Add carbon：By the Na obtained by 0.15g4Ti9O20It is stirred well to and is uniformly mixed with the glucose of 25ml 0.5mol/L, treated
Reactant；
Secondary response：It treats that reactant is moved in the autoclave of polytetrafluoroethyllining lining by what is obtained, is put into insulating box,
Hydro-thermal reaction is carried out at 160 DEG C 4 hours, obtain secondary response product；
Redrying：Gained secondary response product is first washed with deionized, is then washed with absolute ethyl alcohol, is transferred to later
50~90 DEG C of dryings at least 2 hours, obtain dried object in insulating box；
Heat treatment：By dried object under conditions of nitrogen protection, 400 DEG C are warming up to the heating rate of 5 DEG C/min, is then existed
400 DEG C keep the temperature 4 hours, obtain Na after reaction4Ti9O20With the compound of carbon.
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| CN112707498A (en) * | 2020-12-31 | 2021-04-27 | 南京师范大学 | Device for relieving salt accumulation of anaerobic forward osmosis membrane bioreactor and controlling pollutants and using method |
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| CN111689624A (en) * | 2020-05-11 | 2020-09-22 | 中南大学 | Application method of carbon-based metal vanadium monoatomic material in ammonia nitrogen wastewater treatment |
| CN111729623A (en) * | 2020-05-24 | 2020-10-02 | 同济大学 | Preparation method and application of three-dimensional copper ferricyanide composite polypyrrole/polyvinyl alcohol conductive hydrogel material |
| CN112707498A (en) * | 2020-12-31 | 2021-04-27 | 南京师范大学 | Device for relieving salt accumulation of anaerobic forward osmosis membrane bioreactor and controlling pollutants and using method |
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