CN104037428A - Direct methanol fuel cell with alloy-TiO2 nanotube/Ti anode and preparation method thereof - Google Patents
Direct methanol fuel cell with alloy-TiO2 nanotube/Ti anode and preparation method thereof Download PDFInfo
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- CN104037428A CN104037428A CN201410191708.XA CN201410191708A CN104037428A CN 104037428 A CN104037428 A CN 104037428A CN 201410191708 A CN201410191708 A CN 201410191708A CN 104037428 A CN104037428 A CN 104037428A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a direct methanol fuel cell with alloy-TiO2 nanotube/Ti anode and a preparation method thereof. The direct methanol fuel cell comprises a cell housing, the cell housing is inside provided with a membrane electrode, an air chamber is arranged between the housing and the membrane electrode, the membrane electrode is inside provided with an electrolyte chamber, and the membrane electrode successively comprises a cathode diffusion layer, a cathode catalyst layer, a Nafion membrane, a porous titanium pipe, a TiO2 nanotube and a nanometer alloy layer formed through electroplating deposition; the cathode diffusion layer is connected with the cell housing via welding points and is arranged as a cathode output terminal, and an anode diffusion layer is connected with the cell housing via welding points and is arranged as an anode output terminal; a position, close to the electrolyte chamber, on the housing is provided with a feeding hole and a feeding sealing cover; a position, close to the air chamber, of the housing is provided with an air circulation hole; a position, close to the air chamber, at the bottom of the housing is provided with a water discharging hole; and a position, close to the anode diffusion layer, at the bottom of the housing is provided with a CO2 discharging hole. According to the direct methanol fuel cell, the catalytic oxidation performance and the CO-poisoning resistance of a TiO2 composite catalyst on methanol are improved, and alloy-TiO2 nanotube/Ti can be directly used as the anode of a direct methanol fuel cell and helps to improve the cell performances.
Description
Technical field
The present invention relates to a kind of direct methanol fuel cell.
Background technology
Direct methanol fuel cell (Direct Methanol Fuel Cell, DMFC) have that less energy consumption, energy density are high, methyl alcohol source is abundant, low price, system are simple, move convenient and low noise advantages, be considered to future automobile power and the most promising chemical power source of other vehicles, cause people's extensive concern.One of material of DMFC most critical is electrode catalyst, and it directly affects performance, stability, useful life and the manufacturing cost of battery.Precious metals pt (is less than 80 DEG C) and has excellent catalytic performance under cryogenic conditions, the electrode catalyst of DMFC is all taking Pt as main component at present, wherein PtRu catalyst has stronger anti-CO poisoning performance and the catalytic activity of Geng Gao than pure Pt, be considered to the catalyst of current DMFC the best, but due to defects such as it is expensive, Ru Yi Rong, the utilance in DMFC does not also reach business-like requirement.People have carried out large quantity research and have prepared multiplex catalyst to improve its catalytic activity, improve resisting CO poison ability.TiO
2doping is as PtRuTiO
x/ C and Au/TiO
2ptRu catalyst or as carrier as PtNi/TiO
2, PdAg/TiO
2, PdNi/TiO
2deng, can reduce the consumption of precious metals pt in catalyst or prepare non-platinum catalyst, reduce catalyst manufacturing cost, improve catalytic performance and resisting CO poison ability, there is application prospect.PdNi alloy, PdCo alloy, RuNi alloy, RuAg alloy, PdAg alloy etc. deposit to TiO
2nanotube surface, alloy-TiO
2nanotube/Ti, as direct methanol fuel cell anode, has good catalytic performance and resisting CO poison performance to methyl alcohol, have not been reported.
Summary of the invention
The object of the present invention is to provide one can reduce direct methanol fuel cell catalyst cost, improve the alloy-TiO of its catalytic activity and resisting CO poison ability
2nanotube/Ti anode direct methanol fuel cell.
Technical solution of the present invention is:
A kind of alloy-TiO
2nanotube/Ti anode direct methanol fuel cell, comprises outside battery
Shell (1), arranges membrane electrode (4) in battery case, shell (1) and membrane electrode (4) it
Between be air chamber (2), electrolyte liquor chamber (6) is set in membrane electrode (4), it is characterized in that:
Described membrane electrode (4) cathode diffusion layer (7), cathode catalyst layer (8), Nafion film (9) and alloy-TiO successively from outside to inside
2nanotube/Ti anode, described alloy-TiO
2nanotube/Ti anode is by POROUS TITANIUM pipe (10), TiO
2nanoalloy layer (12) composition of nanotube (11), electroplating deposition; Alloy-TiO
2first nanotube/Ti anode forms TiO by the anodic oxidation of POROUS TITANIUM inner tube layer
2nanotube, then electroplating deposition Nanoalloy forms;
Cathode diffusion layer (8) is connected and is set to cathode end (3) by pad with battery case (1), anode diffusion layer is connected and is set to anode output end (5) by pad with battery case, the electrolyte liquor chamber position of shell arranges charging aperture (15) and reinforced seal cover (16), air chamber (2) position of shell arranges air stream through hole (13), air chamber (2) bottom of shell arranges water discharge orifice (14), and the anode diffusion layer bottom of shell arranges CO2 discharge orifice (17).
Further: described cathode end (3) adopts stainless steel, copper or titanium material, anode output end (5) adopts stainless steel, copper or titanium material; Reinforced seal cover (16) adopts polytetrafluoroethylene.
For the alloy-TiO of described direct methanol fuel cell
2the preparation method of nanotube/Ti anode, is characterized in that, comprises the steps:
(1) pre-treatment of POROUS TITANIUM pipe: ultrasonic oil removing 15 minutes in acetone, methyl alcohol or ethanol clean; The CrO of 400 g/L
3h with 350 g/L
2sO
4process 3 minutes, redistilled water ultrasonic cleaning 3 times, the HF of 1 mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried;
(2) TiO
2the preparation of nanotube/Ti: the POROUS TITANIUM outer tube layer of handling well is carried out carrying out anodic oxidation after insulation processing in electrolyte; The HF of the composition of electrolyte: 0.5%-1%, the H of 1mol/L
2sO
4; Electrolytic potential 20 V, electrolysis time 30-120 minute; Electrolysis is complete, and deionized water washing, dries, and in Muffle furnace, 500 DEG C of roastings obtain TiO for 3 hours
2nanotube/Ti;
(3) alloy-TiO
2the preparation of nanotube/Ti anode: by the TiO preparing
2nanotube/Ti electroplates as negative electrode, at TiO
2the plating inner surface depositing nano alloy of nanotube/Ti, obtains alloy-TiO
2nanotube/Ti anode; Described alloy is PdNi alloy, PdCo alloy, RuNi alloy, RuAg alloy or PdAg alloy.
The preparation method who is used for the membrane electrode of described direct methanol fuel cell, is characterized in that, comprises the steps:
(1) pre-treatment of POROUS TITANIUM pipe: ultrasonic oil removing 15 minutes in acetone, methyl alcohol or ethanol clean; The CrO of 400 g/L
3h with 350 g/L
2sO
4process 3 minutes, redistilled water ultrasonic cleaning 3 times, the HF of 1 mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried;
(2) TiO
2the preparation of nanotube/Ti: the POROUS TITANIUM outer tube layer of handling well is carried out carrying out anodic oxidation after insulation processing in electrolyte; The HF of the composition of electrolyte: 0.5%-1%, the H of 1mol/L
2sO
4; Electrolytic potential 20 V, electrolysis time 30-120 minute; Electrolysis is complete, and deionized water washing, dries, and in Muffle furnace, 500 DEG C of roastings obtain TiO for 3 hours
2nanotube/Ti;
(3) alloy-TiO
2the preparation of nanotube/Ti anode: by the TiO preparing
2nanotube/Ti electroplates as negative electrode, at TiO
2the plating inner surface depositing nano alloy of nanotube/Ti, obtains alloy-TiO
2nanotube/Ti anode; Described alloy is PdNi alloy, PdCo alloy, RuNi alloy, RuAg alloy or PdAg alloy;
(4) preparation of cathode catalyst layer: cathod catalyst pulp spraying is coated onto to PTFE film surface;
(5) preparation of membrane electrode: alloy-TiO2 nanotube/Ti anode and cathod catalyst are placed on to Nafion film both sides, and hot pressing, throws off PTFE diaphragm, adds cathode diffusion layer hot pressing and obtains membrane electrode.
Beneficial effect of the present invention is: the present invention first forms nanotube with the oxidation of POROUS TITANIUM tube anode on surface, then electroplating deposition Nanoalloy forms.After the oxidizing roasting of POROUS TITANIUM tube anode, form the TiO of skim high-ratio surface on titanium plate surface
2nanotube, TiO
2nanotube surface electroplating deposition Nanoalloy can improve TiO
2the conductivity of nanotube and Nanoalloy are to TiO
2synergy improve TiO
2to the catalytic oxidation performance of methyl alcohol, meanwhile, the intermediate products such as the CO that methanol oxidation produces are adsorbed, transfer to alloy-TiO
2nanotube surface, and be end product CO by deep oxidation
2, can improve the resisting CO poison ability of catalyst, because the price of alloy is far below the noble metal such as Pt, Ru, and the alloy of electroplating deposition is at TiO
2the amount of nanotube surface is less, therefore can greatly reduce the cost of catalyst, alloy-TiO
2nanotube/Ti, as direct methanol fuel cell anode, can improve battery performance.This battery can be used as the electrokinetic cell of mancarried device and motorcycle, the automobiles etc. such as mobile phone, notebook computer, mobile phone, realizes commercial application.The requirement that can use according to reality, both can make micro fuel cell and battery pack, also can make large-scale electricity fuel cell.According to practical application needs, battery can be made into various shapes.
Brief description of the drawings
Fig. 1 is the configuration diagram of one embodiment of the invention.
Fig. 2 is the structure chart of one embodiment of the invention.
Fig. 3 is the section of structure of membrane electrode 4.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1:
Alloy-TiO
2nanotube/Ti anode direct methanol fuel cell, comprise battery case 1, membrane electrode 4 is set in battery case, it between shell and membrane electrode, is air chamber 2, electrolyte liquor chamber 6 is set in membrane electrode, and membrane electrode is cathode diffusion layer 7, cathode catalyst layer 8, Nafion film 9, POROUS TITANIUM pipe 10, TiO from outside to inside
2the Nanoalloy layer 12 of nanotube 11, electroplating deposition, cathode diffusion layer is connected and is set to cathode end 3 by pad with battery case, anode diffusion layer is connected and is set to anode output end 5 by pad with battery case, the electrolyte liquor chamber position of shell arranges charging aperture 15, reinforced seal cover 16, the air chamber position of shell arranges air stream through hole 13, and the air chamber bottom of shell arranges water discharge orifice 14, and the anode diffusion layer bottom of shell arranges CO
2discharge orifice 17.
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
(1) pre-treatment of POROUS TITANIUM pipe: ultrasonic oil removing 15 minutes in acetone, methyl alcohol or ethanol clean.The CrO of 400 g/L
3h with 350 g/L
2sO
4process 3 minutes, redistilled water ultrasonic cleaning 3 times, the HF of 1 mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried.
(2) TiO
2the preparation of nanotube/Ti: the POROUS TITANIUM outer tube layer of handling well is pasted to the methods such as insulating tape and carried out carrying out anodic oxidation after insulation processing in electrolyte.The HF of the composition of electrolyte: 0.5%-1%, the H of 1mol/L
2sO
4.Electrolytic potential 20 V, electrolysis time 30-120 minute.Electrolysis is complete, and deionized water washing, dries, and in Muffle furnace, 500-600 DEG C of roasting obtains TiO for 3 hours
2nanotube/Ti.
(3) alloy-TiO
2the preparation of nanotube/Ti anode: by the TiO preparing
2nanotube/Ti electroplates as negative electrode.
At TiO
2the plating inner surface depositing nano alloy of nanotube/Ti is PdNi alloy.
The composition of electroplate liquid:
NiSO
4·6H
2O 250 g/L
PdCl
2 1 g/L
H
3BO
3 20g/L
PH: 4.4
T: room temperature
Current density: 5 mA/cm
2
T:120 minute
Electroplate completely, deionized water washing, dries,, obtain PdNi-TiO
2nanotube/Ti anode.
Embodiment 2:
At TiO
2the plating inner surface depositing nano alloy of nanotube/Ti is PdAg alloy.
The composition of electroplate liquid:
AgNO
3 0.01 mol/L
Pd(NO)
2 0.01 mol/L
H
3BO
3 20g/L
PH: 4.4
T: room temperature
Current density: 5 mA/cm
2
t: 120 min
Electroplate completely, deionized water washing, dries, and obtains PdAg-TiO
2nanotube/Ti anode.The other the same as in Example 1.
Embodiment 3:
At TiO
2the plating inner surface depositing nano alloy of nanotube/Ti is RuNi alloy.
The composition of electroplate liquid:
NiSO
4·6H
2O 250 g/L
RuCl
3 1 g/L
H
3BO
3 20g/L
PH 4.4
T room temperature
Current density: 5 mA/cm
2
t 120 min
Electroplate completely, deionized water washing, dries, and obtains RuNi-TiO
2nanotube/Ti anode.
Embodiment 4:
At TiO
2the plating inner surface depositing nano alloy of nanotube/Ti is PdRu alloy.
The composition of electroplate liquid:
PdCl
2 0.01 mol/L
RuCl
3 0.01 mol/L
H
3BO
3 20g/L
PH: 4.4
T: room temperature
Current density: 5 mA/cm
2
t: 120 min
Electroplate completely, deionized water washing, dries, and obtains PdRu-TiO
2nanotube/Ti anode.
Embodiment 5:
At TiO
2the plating inner surface depositing nano alloy of nanotube/Ti is PdCo alloy.
The composition of electroplate liquid:
PdCl
2 0.01 mol/L
Co Cl
2 0.01 mol/L
H
3BO
3 20g/L
PH: 4.4
T: room temperature
Current density: 5 mA/cm
2
t: 30-90 min
Electroplate completely, deionized water washing, dries, and obtains PdCo-TiO
2nanotube/Ti anode.
Claims (4)
1. an alloy-TiO
2nanotube/Ti anode direct methanol fuel cell, comprises battery case (1), and membrane electrode (4) is set in battery case, between shell (1) and membrane electrode (4), is air chamber (2), and electrolyte liquor chamber (6) is set in membrane electrode (4), it is characterized in that:
Described membrane electrode (4) cathode diffusion layer (7), cathode catalyst layer (8), Nafion film (9) and alloy-TiO successively from outside to inside
2nanotube/Ti anode, described alloy-TiO
2nanotube/Ti anode is by POROUS TITANIUM pipe (10), TiO
2nanoalloy layer (12) composition of nanotube (11), electroplating deposition; Alloy-TiO
2first nanotube/Ti anode forms TiO by the anodic oxidation of POROUS TITANIUM inner tube layer
2nanotube, then electroplating deposition Nanoalloy forms;
Cathode diffusion layer (8) is connected and is set to cathode end (3) by pad with battery case (1), anode diffusion layer is connected and is set to anode output end (5) by pad with battery case, the electrolyte liquor chamber position of shell arranges charging aperture (15) and reinforced seal cover (16), air chamber (2) position of shell arranges air stream through hole (13), air chamber (2) bottom of shell arranges water discharge orifice (14), and the anode diffusion layer bottom of shell arranges CO2 discharge orifice (17).
2. a kind of alloy-TiO according to claim 1
2nanotube/Ti anode direct methanol fuel cell, is characterized in that: described cathode end (3) adopts stainless steel, copper or titanium material, and anode output end (5) adopts stainless steel, copper or titanium material; Reinforced seal cover (16) adopts polytetrafluoroethylene.
3. for the alloy-TiO of direct methanol fuel cell described in claim 1
2the preparation method of nanotube/Ti anode, is characterized in that, comprises the steps:
(1) pre-treatment of POROUS TITANIUM pipe: ultrasonic oil removing 15 minutes in acetone, methyl alcohol or ethanol clean; The CrO of 400 g/L
3h with 350 g/L
2sO
4process 3 minutes, redistilled water ultrasonic cleaning 3 times, the HF of 1 mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried;
(2) TiO
2the preparation of nanotube/Ti: the POROUS TITANIUM outer tube layer of handling well is carried out carrying out anodic oxidation after insulation processing in electrolyte; The HF of the composition of electrolyte: 0.5%-1%, the H of 1mol/L
2sO
4; Electrolytic potential 20 V, electrolysis time 30-120 minute; Electrolysis is complete, and deionized water washing, dries, and in Muffle furnace, 500 DEG C of roastings obtain TiO for 3 hours
2nanotube/Ti;
(3) alloy-TiO
2the preparation of nanotube/Ti anode: by the TiO preparing
2nanotube/Ti electroplates as negative electrode, at TiO
2the plating inner surface depositing nano alloy of nanotube/Ti, obtains alloy-TiO
2nanotube/Ti anode; Described alloy is PdNi alloy, PdCo alloy, RuNi alloy, RuAg alloy or PdAg alloy.
4. for the preparation method of the membrane electrode of direct methanol fuel cell described in claim 1, it is characterized in that, comprise the steps:
(1) pre-treatment of POROUS TITANIUM pipe: ultrasonic oil removing 15 minutes in acetone, methyl alcohol or ethanol clean; The CrO of 400 g/L
3h with 350 g/L
2sO
4process 3 minutes, redistilled water ultrasonic cleaning 3 times, the HF of 1 mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried;
(2) TiO
2the preparation of nanotube/Ti: the POROUS TITANIUM outer tube layer of handling well is carried out carrying out anodic oxidation after insulation processing in electrolyte; The HF of the composition of electrolyte: 0.5%-1%, the H of 1mol/L
2sO
4; Electrolytic potential 20 V, electrolysis time 30-120 minute; Electrolysis is complete, and deionized water washing, dries, and in Muffle furnace, 500 DEG C of roastings obtain TiO for 3 hours
2nanotube/Ti;
(3) alloy-TiO
2the preparation of nanotube/Ti anode: by the TiO preparing
2nanotube/Ti electroplates as negative electrode, at TiO
2the plating inner surface depositing nano alloy of nanotube/Ti, obtains alloy-TiO
2nanotube/Ti anode; Described alloy is PdNi alloy, PdCo alloy, RuNi alloy, RuAg alloy or PdAg alloy;
(4) preparation of cathode catalyst layer: cathod catalyst pulp spraying is coated onto to PTFE film surface;
(5) preparation of membrane electrode: alloy-TiO2 nanotube/Ti anode and cathod catalyst are placed on to Nafion film both sides, and hot pressing, throws off PTFE diaphragm, adds cathode diffusion layer hot pressing and obtains membrane electrode.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410191708.XA CN104037428B (en) | 2014-05-07 | 2014-05-07 | Direct methanol fuel cell with alloy-TiO2 nanotube/Ti anode and preparation method thereof |
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|---|---|---|---|
| CN201410191708.XA CN104037428B (en) | 2014-05-07 | 2014-05-07 | Direct methanol fuel cell with alloy-TiO2 nanotube/Ti anode and preparation method thereof |
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| CN104037428B CN104037428B (en) | 2017-02-15 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186205A (en) * | 2016-07-18 | 2016-12-07 | 南京理工大学 | A kind of micropore titanio tubular type multidimensional nano-pore embeds stannum antimony membrane electrode and preparation method thereof |
| CN108383214A (en) * | 2018-05-21 | 2018-08-10 | 南通大学 | A kind of photovoltaic electro-catalysis treatment of Organic Wastewater reactor and its anode preparation method |
| CN111029594A (en) * | 2019-12-31 | 2020-04-17 | 南通大学 | Black phosphorus-TiO2nanotube/Ti anode direct methanol fuel cell |
| CN111141788A (en) * | 2019-12-31 | 2020-05-12 | 南通大学 | Black phosphorus-TiO2Nano tube/Ti sensitive electrode hydrogen sulfide sensor |
| CN112107996A (en) * | 2020-09-14 | 2020-12-22 | 南通大学 | Air filter and preparation method thereof |
| CN112146197A (en) * | 2020-09-14 | 2020-12-29 | 南通大学 | Noise elimination disinfection self-purification air purifier |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101335362A (en) * | 2008-05-29 | 2008-12-31 | 南通大学 | Circular direct methanol fuel cell of high performance and low cost |
| CN102553649A (en) * | 2011-12-26 | 2012-07-11 | 河海大学 | 17beta-estradiol molecular imprinted silver-doped TiO2 nanotube and preparation method thereof |
| CN102836708A (en) * | 2012-09-06 | 2012-12-26 | 南通大学 | Preparation method of PdAg/TiO2 nanotube direct methanol fuel cell anode catalyst |
-
2014
- 2014-05-07 CN CN201410191708.XA patent/CN104037428B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101335362A (en) * | 2008-05-29 | 2008-12-31 | 南通大学 | Circular direct methanol fuel cell of high performance and low cost |
| CN102553649A (en) * | 2011-12-26 | 2012-07-11 | 河海大学 | 17beta-estradiol molecular imprinted silver-doped TiO2 nanotube and preparation method thereof |
| CN102836708A (en) * | 2012-09-06 | 2012-12-26 | 南通大学 | Preparation method of PdAg/TiO2 nanotube direct methanol fuel cell anode catalyst |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186205A (en) * | 2016-07-18 | 2016-12-07 | 南京理工大学 | A kind of micropore titanio tubular type multidimensional nano-pore embeds stannum antimony membrane electrode and preparation method thereof |
| CN108383214A (en) * | 2018-05-21 | 2018-08-10 | 南通大学 | A kind of photovoltaic electro-catalysis treatment of Organic Wastewater reactor and its anode preparation method |
| CN108383214B (en) * | 2018-05-21 | 2024-04-05 | 南通大学 | Photovoltaic electro-catalysis organic wastewater treatment reactor and anode preparation method thereof |
| CN111029594A (en) * | 2019-12-31 | 2020-04-17 | 南通大学 | Black phosphorus-TiO2nanotube/Ti anode direct methanol fuel cell |
| CN111141788A (en) * | 2019-12-31 | 2020-05-12 | 南通大学 | Black phosphorus-TiO2Nano tube/Ti sensitive electrode hydrogen sulfide sensor |
| CN111141788B (en) * | 2019-12-31 | 2021-08-03 | 南通大学 | Black phosphorus-TiO2Nano tube/Ti sensitive electrode hydrogen sulfide sensor |
| CN111029594B (en) * | 2019-12-31 | 2022-05-17 | 南通大学 | Black phosphorus-TiO2nanotube/Ti anode direct methanol fuel cell |
| CN112107996A (en) * | 2020-09-14 | 2020-12-22 | 南通大学 | Air filter and preparation method thereof |
| CN112146197A (en) * | 2020-09-14 | 2020-12-29 | 南通大学 | Noise elimination disinfection self-purification air purifier |
| CN112146197B (en) * | 2020-09-14 | 2022-03-11 | 南通大学 | Noise elimination disinfection self-purification air purifier |
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| CN104037428B (en) | 2017-02-15 |
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