CN106654163A - Preparation method of cathode of seawater dissolved oxygen battery - Google Patents
Preparation method of cathode of seawater dissolved oxygen battery Download PDFInfo
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- CN106654163A CN106654163A CN201611243479.7A CN201611243479A CN106654163A CN 106654163 A CN106654163 A CN 106654163A CN 201611243479 A CN201611243479 A CN 201611243479A CN 106654163 A CN106654163 A CN 106654163A
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- dissolved oxygen
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- seawater
- seawater dissolved
- nitrogen
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000001301 oxygen Substances 0.000 title claims abstract description 53
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 53
- 239000013535 sea water Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 49
- 239000004917 carbon fiber Substances 0.000 claims abstract description 49
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 10
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 39
- 230000008569 process Effects 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 42
- 230000000694 effects Effects 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 230000005611 electricity Effects 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to a preparation method of a cathode of a seawater dissolved oxygen battery. The invention belongs to the technical field of electric energy materials. A preparation method of a seawater dissolved oxygen battery cathode is characterized by comprising the following steps: the preparation method of the cathode of the seawater dissolved oxygen battery comprises the steps of regarding the cathode of the seawater dissolved oxygen battery as a core-shell structure consisting of a matrix and a surface active layer, wherein the shell of the surface active layer is three-dimensionally and omnidirectionally attached to the surface of the matrix core; the substrate core is a PAN carbon fiber material, and the surface active layer shell is a product obtained on the surface of the PAN carbon fiber body by carrying out nitrogen-doped surface modification treatment directly in a nitrogen-containing atmosphere through heat treatment. The invention has the advantages of high catalytic activity, high electrochemical performance, simple process, high speed, high efficiency, low cost and the like.
Description
Technical field
The invention belongs to electric energy field of material technology, more particularly to a kind of preparation side of seawater dissolved oxygen cell cathode
Method.
Background technology
At present, either deep-sea detecting, underwater information system Construction, or ocean scientific investigation, search and rescue etc. under water, all need
Deep sea equipment is wanted, and long-term, the stable operation equipped be unable to do without high-energy-density, the support of high security electric energy.Due to ocean
The particularity of environment, battery becomes the sole power energy of its underwater operation.Conventional one-shot battery such as lithium thionyl chloride cell etc.
Security in the seawater has much room for improvement, and conventional secondary cell such as lithium ion battery etc. is low due to its specific energy, causes it to use
Life-span is shorter；And this two classes battery is when in use for the pressure in waterproof and resistance to deep-sea, must also be placed in thick and heavy pressure
In container, the weight and technical difficulty of system is virtually increased.And a kind of new seawater dissolved oxygen battery is adopted due to it
Natural seawater is electrolyte, without the need for carrying electrolyte solution；Dissolved Oxygen in Seawater is adopted for cathode reaction active material, nothing
Active material of cathode need to be carried；Using open battery structure, without the need for pressure vessel protection, therefore with energy density height, peace
Quan Xinggao, overlong service life, it is with low cost the features such as, have broad application prospects in marine settings application.
Negative electrode is the most important components of seawater dissolved oxygen battery, is to determine power of battery output characteristics, life-span, reliability
The key factor of property etc., it is desirable to which it has excellent electro catalytic activity, electric conductivity, stability and mechanical strength etc..In recent years, business
Industry polyacrylonitrile carbon fiber has the advantages that good conductivity, low price, Stability Analysis of Structures, corrosion-resistant as a kind of micron order material
It is widely used and does the electrode of dissolved oxygen seawater battery, flow battery, fuel cell, metal-air battery, ultracapacitor etc.
Material.But if the carbon fibre material of long time without surface modification treatment is directly used as into seawater dissolved oxygen battery cathode material, by
In itself surface is inert, electro catalytic activity is low, the concentration of another aspect Dissolved Oxygen in Seawater is especially low, causes dissolved oxygen cloudy
Pole reduction reaction electrocatalysis characteristic is low, can only work under extremely low current density, it is impossible to the higher current density of load, causes electricity
The power density output characteristics in pond is poor, needs the power demand that seawater battery could be met with substantial amounts of material with carbon element, will certainly increase
The volume and weight of big battery.Therefore need to carry out surface modification treatment to it.The surface modification treatment of current carbon fibre material
Method mainly has microwave combustion method method, anodizing, electrochemical process, plasma method etc..
CN105951216A discloses a kind of preparation method of three-dimensional nitrogen-doped carbon fiber, and the method is first by chopped carbon
Fiber is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), and 1-4 hours are reacted under 60 ゜ C, obtains being acidified carbon fiber；Then will
Acidifying carbon fiber carries out the microwave treatment of short time, obtains expanded carbon fiber, after then mixing with the solid ammonium salt such as ammonium chloride again
A few hours are heat-treated in micro-wave oven high temperature, nitrogen-doped carbon fiber is obtained.The method is applied to chopped carbon fiber, it is therefore an objective to improve
The structural stability of material.Further, since employing the concentrated sulfuric acid and red fuming nitric acid (RFNA), corrosivity is strong, and security is poor, to operation and equipment
Requirement it is higher.
CN105484012A discloses a kind of polyacrylonitrile carbon fiber surface treatment method and device, the process employs two
Section anode electrolysis oxidation processes mode, carries out oxidation processes, then through ultrasonic clear first by carbon fiber in acidic electrolysis groove
Wash, after roller is dried, then second oxidation processes carried out in alkaline electrolyte.The method technique is more complicated, and purpose is
Improve the interlaminar shear strength of material.
WO2014/127501A1 discloses a kind of oxygen and the fine carbon fiber of nitrogen co-doped polypropylene and preparation method thereof, should
Method is that polyacrylonitrile carbon fiber is placed in electrolyte solution, by controlling total electricity, through electrochemical oxidation and electrochemistry
After iterative cycles between reduction are processed, oxygen and nitrogen co-doped product are obtained.Although the method improves the electricity of carbon fiber and urges
Change activity, but the comparatively laborious complexity of handling process, it is relatively costly.
CN103361768A discloses a kind of polypropylene-base carbon fiber surface modification method, and the method is by carbon fiber first
Matrix high temperature cabonization at 1500 DEG C, then carries out corona treatment in atmosphere of inert gases, next again by atomization
Device carries out atomization process.The method complex process, equipment cost is high, and has directionality when processing, and the carbon of gained is fine
Tie up full surface uniformity consistency poor, therefore be restricted in commercial Application.
The content of the invention
The present invention provides a kind of system of seawater dissolved oxygen cell cathode to solve technical problem present in known technology
Preparation Method.
It is an object of the invention to provide it is a kind of have catalysis activity height, chemical property height, process is simple, rapidly and efficiently,
The preparation method of the seawater dissolved oxygen cell cathode of with low cost the features such as.
Seawater dissolved oxygen cell cathode of the present invention can regard " nucleocapsid " being made up of matrix and surface-active layer as and tie
Structure, surface-active layer this layer " shell " 3 D stereo is comprehensive is attached on the surface of matrix " core ".Wherein, matrix " core " is PAN
Carbon fibre material；Surface-active layer " shell " is directly by carbon fiber body under nitrogen containing atmosphere, by heat treatment N doping to be carried out
The product obtained on its surface after surface modification treatment.
The present invention based on PAN carbon fibre materials, under nitrogen containing atmosphere environment, heating rate be 3-15 DEG C/min, in
0.5-6h is heat-treated at 650 DEG C -950 DEG C, the nitrogen-doped modified PAN carbon fibers of 3 D stereo are obtained after Temperature fall cooling
Negative electrode.Nitrogen containing atmosphere environment is the gas containing nitrogen, can be mixed gas, the ammonia of nitrogen, ammonia or nitrogen and inert gas
At least one in the mixed gas of gas and inert gas.Inert gas is argon gas or at least one in helium.
Seawater dissolved oxygen cell cathode matrix uses polyacrylonitrile (PAN) carbon fiber wire beam material.As needed, should
The shape of negative electrode can be made variously-shaped, it is preferable that the negative electrode be shaped as turn round brush.For the size of negative electrode, can
To be designed and select according to the occasion of battery applications and the needs of watt level.
In the preparation method that the present invention is provided, first PAN carbon fibre tow design of material can be prepared into into required size
Torsion brush negative electrode, gas phase heat treatment is then carried out to the negative electrode again, obtain surface-active layer；Or first to PAN carbon fibers
Strand material carries out gas phase heat treatment, obtains surface-active layer, then cloudy further according to the torsion brush for being prepared into required size is needed
Pole.
The preparation method of seawater dissolved oxygen cell cathode of the present invention is adopted the technical scheme that：A kind of seawater dissolved oxygen electricity
The preparation method of pool cathode, is characterized in：The preparation method of seawater dissolved oxygen cell cathode is by seawater dissolved oxygen cell cathode
Regard a core shell structure being made up of matrix and surface-active layer as, this layer of shell 3 D stereo of surface-active layer is comprehensive to be attached to
On the surface of matrix core；Matrix core is PAN carbon fibre materials, and surface-active layer shell is directly nitrogenous by PAN carbon fiber bodies
Under atmosphere, the product for carrying out being obtained on its surface after N doping surface modification treatment by heat treatment.
The preparation method of seawater dissolved oxygen cell cathode of the present invention can also be adopted the following technical scheme that：
The preparation method of described seawater dissolved oxygen cell cathode, is characterized in：Surface-active layer shell is with PAN carbon fibers
Based on material, under nitrogen containing atmosphere environment, heating rate is 3-15 DEG C/min, at 650 DEG C -950 DEG C is heat-treated 0.5-
6h, after Temperature fall cooling the nitrogen-doped modified PAN carbon-fiber cathodes of 3 D stereo are obtained.
The preparation method of described seawater dissolved oxygen cell cathode, is characterized in：Nitrogen containing atmosphere is the gas containing nitrogen, is
At least one in the mixed gas of the mixed gas, ammonia and inert gas of nitrogen, ammonia or nitrogen and inert gas.
The preparation method of described seawater dissolved oxygen cell cathode, is characterized in：Inert gas is in argon gas or helium
It is at least one.
The preparation method of described seawater dissolved oxygen cell cathode, is characterized in：PAN carbon fibers are polyacrylonitrile (PAN) carbon
Fibre bundle material.
The present invention has the advantages and positive effects that：
The preparation method of seawater dissolved oxygen cell cathode as a result of the brand-new technical scheme of the present invention, with prior art
Compare, the present invention has following evident characteristic：
1. N doping surface modifying method is adopted, and PAN carbon fibre material matrixes, can be in material with carbon element in heat treatment process
The active layer of Surface Creation nitrogen-containing functional group, because the atomic surface hybridized orbit state caused by nitrogen-doped carbon can be carried significantly
Catalysis activity is risen, therefore more dissolved oxygen cathodic reduction reaction active sites can be introduced to electrode surface, so as to effectively carry
The high electro catalytic activity performance of PAN carbon-fiber cathodes.
2. vapor phase method is adopted, can be comprehensive on PAN carbon-fiber cathode 3 D stereos surface while generating uniformity
Active layer, increased the effecting reaction surface area of Dissolved Oxygen in Seawater electrochemical reaction, higher power density can be exported,
So as to be effectively improved the chemical property of PAN carbon-fiber cathodes.
3. a step gas phase heat treating process is adopted, technique is simplified, process costs are reduced, it is easy to operate, rapidly and efficiently, easily
In industrialized production.
Description of the drawings
Fig. 1 is cloudy for the seawater dissolved oxygen battery PAN carbon fibers after N doping surface modification treatment that the present invention is provided
" nucleocapsid " structural representation of pole；
1 is " core "-PAN carbon fiber substrates in figure, and 2 is to generate in matrix surface after the doping of " shell "-gas phase heat treatment nitrogen
Nitrogen-containing functional group surface-active layer.
Fig. 2 be the embodiment of the present invention 1 in through gas phase heat treatment nitrogen doping vario-property process after PAN carbon-fiber cathodes with than
Polarization curve of the PAN carbon fiber blank negative electrode untreated compared with example under different constant current densities；
In figure, a is the electrode after the process of the N doping of embodiment 1, and b is the untreated electrode of comparative example.
Fig. 3 be the embodiment of the present invention 2 in through gas phase heat treatment nitrogen doping vario-property process after PAN carbon-fiber cathodes with than
Polarization curve of the PAN carbon fiber blank negative electrode untreated compared with example under different constant current densities；
In figure, a is the electrode after the process of the N doping of embodiment 2, and b is the untreated electrode of comparative example.
Specific embodiment
For the content of the invention, feature and effect of the present invention can be further appreciated that, following examples are hereby enumerated, and coordinate accompanying drawing
Describe in detail as follows：
Embodiment 1
The preparation method of seawater dissolved oxygen cell cathode, seawater dissolved oxygen cell cathode is regarded as by matrix and surface-active
" nucleocapsid " structure for layer composition, this comprehensive surface for being attached to matrix " core " of layer " shell " 3 D stereo of surface-active layer
On；Matrix " core " is PAN carbon fibre materials, and surface-active layer " shell " is directly by PAN carbon fibers body under nitrogen containing atmosphere, to lead to
Overheating Treatment carries out the product obtained on its surface after N doping surface modification treatment.
The present embodiment specific implementation process：
The torsion brush PAN carbon-fiber cathode of a diameter of 3cm, length for 7cm is put in tube furnace, in 92%Ar+8%
NH3Mixed atmosphere protection under, make tube furnace be warming up to 700 DEG C with the heating rate of 5 DEG C/min, be incubated 3 hours, Temperature fall
Cooling, you can obtain the seawater dissolved oxygen battery PAN carbon-fiber cathodes after N doping is processed.
To test the performance of the seawater dissolved oxygen cell cathode of gas phase heat treatment nitrogen doping vario-property, prepared by embodiment 1
PAN carbon-fiber cathodes have carried out the test of three-electrode system galvanostatic polarization curve.It is cloudy with the PAN carbon fibers processed through N doping
Extremely working electrode, used as to electrode, saturated calomel electrode is used as reference electrode, the electrochemical test of employing for AZ31 magnesium alloys
Device is blue electricity battery test system.Electrolyte solution be 3.5%NaCl simulated seawater solution, flow velocity 5cm/s, oxygen in solution
Concentration is 6.8ppm.Working electrode is tested respectively under the constant current of 10mA/g, 50mA/g, 100mA/g, record electricity
Position and the relation of time.For seawater dissolved oxygen cell cathode, in three electrode test systems, its steady operation current potential is got over
Just, illustrate that it is higher for the reduction reaction electro catalytic activity of cathode oxygen, its electrical property is better.
For the effect of electrode in comparing embodiment 1, by same size and shape but without nitrogen-doped modified process
PAN carbon fibers blank electrode carries out contrast test as comparative example, in above-mentioned three-electrode system.
Fig. 2 be the embodiment of the present invention 1 in through gas phase heat treatment nitrogen doping vario-property process after PAN carbon-fiber cathodes with than
The polarization curve of the PAN carbon fiber blank negative electrode untreated compared with example.It can be seen that untreated carbon is fine
Dimension is under the discharge current density of 10mA/g, and steady operation current potential is low to -0.56V (Vs SCE)；Can not bear 50mA/g,
And the discharge current density under 100mA/g, this shows that its, almost without electrochemical catalysis activity, is not suitable for directly doing seawater molten
The negative electrode of solution oxygen cell；And embodiment 1 after treatment is under 10mA/g current densities during constant current discharge, its steady operation
Current potential is -0.09V (vs.SCE), hence it is evident that shuffled 0.47V；Additionally, embodiment 1 can also bear the higher electricity of 50mA/g, 100mA/g
Discharge under current density, its stable operating voltage is respectively -0.262V and -0.428V (vs.SCE).As can be seen here through the present invention
Embodiment 1 has considerably higher electro catalytic activity to Dissolved Oxygen in Seawater cathodic reduction reaction, can bear higher electric discharge
Current density, exports the operating voltage of corrigendum, such that it is able to make seawater battery export higher discharge energy density.
Embodiment 2
The preparation method of seawater dissolved oxygen cell cathode, seawater dissolved oxygen cell cathode is regarded as by matrix and surface-active
" nucleocapsid " structure for layer composition, this comprehensive surface for being attached to matrix " core " of layer " shell " 3 D stereo of surface-active layer
On；Matrix " core " is PAN carbon fibre materials, and surface-active layer " shell " is directly by PAN carbon fibers body under nitrogen containing atmosphere, to lead to
Overheating Treatment carries out the product obtained on its surface after N doping surface modification treatment.
The present embodiment specific implementation process：
The torsion brush PAN carbon-fiber cathode of a diameter of 3cm, length for 7cm is put in tube furnace, in N2Atmosphere protection
Under, make tube furnace be warming up to 800 ゜ C with the heating rate of 8 DEG C/min, 2 hours are incubated, Temperature fall cooling, you can obtain nitrogen and mix
Live together the seawater dissolved oxygen battery PAN carbon-fiber cathodes after reason.
Fig. 3 be the embodiment of the present invention 2 in through gas phase heat treatment nitrogen doping vario-property process after PAN carbon-fiber cathodes with than
The polarization curve of the PAN carbon fiber blank negative electrode untreated compared with example.It can be seen that untreated carbon is fine
Dimension is under the discharge current density of 10mA/g, and steady operation current potential is low to -0.56V (Vs SCE)；Can not bear 50mA/g,
And the discharge current density under 100mA/g, this shows that its, almost without electrochemical catalysis activity, is not suitable for directly doing seawater molten
The negative electrode of solution oxygen cell；And embodiment 2 after treatment is under 10mA/g current densities during constant current discharge, its steady operation
Current potential is -0.10V (vs.SCE), hence it is evident that shuffled 0.46V；Additionally, embodiment 1 can also bear the higher electricity of 50mA/g, 100mA/g
Discharge under current density, its stable operating voltage is respectively -0.266V and -0.431V (vs.SCE).As can be seen here through the present invention
Embodiment 2 has considerably higher electro catalytic activity to Dissolved Oxygen in Seawater cathodic reduction reaction, can bear higher electric discharge
Current density, exports the operating voltage of corrigendum, such that it is able to make seawater battery export higher discharge energy density.
The present embodiment 1,2 have described catalysis activity height, chemical property height, process is simple, rapidly and efficiently, low cost
It is honest and clean to wait good effect.
Claims (4)
1. a kind of preparation method of seawater dissolved oxygen cell cathode, is characterized in that：The preparation method of seawater dissolved oxygen cell cathode
It is a core shell structure that seawater dissolved oxygen cell cathode is made up of matrix and surface-active layer, this layer of shell three-dimensional of surface-active layer
Stereoscopic and omnibearing is attached on the surface of matrix core；Matrix core is PAN carbon fibre materials, and surface-active layer shell is directly by PAN
Carbon fiber body carries out the product that obtains on its surface after N doping surface modification treatment under nitrogen containing atmosphere by heat treatment.
2. the preparation method of seawater dissolved oxygen cell cathode according to claim 1, is characterized in that：Surface-active layer shell be
Based on PAN carbon fibre materials, under nitrogen containing atmosphere environment, heating rate be 3-15 DEG C/min, at 650 DEG C -950 DEG C
Heat treatment 0.5-6h, after Temperature fall cooling the nitrogen-doped modified PAN carbon-fiber cathodes of 3 D stereo are obtained.
3. the preparation method of seawater dissolved oxygen cell cathode according to claim 1 and 2, is characterized in that：Nitrogen containing atmosphere is
Gas containing nitrogen, is the mixed gas of mixed gas, ammonia and the inert gas of nitrogen, ammonia or nitrogen and inert gas
In at least one.
4. the preparation method of seawater dissolved oxygen cell cathode according to claim 3, is characterized in that：Inert gas is argon gas
Or at least one in helium.
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| CN201611243479.7A CN106654163A (en) | 2016-12-29 | 2016-12-29 | Preparation method of cathode of seawater dissolved oxygen battery |
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| CN201611243479.7A CN106654163A (en) | 2016-12-29 | 2016-12-29 | Preparation method of cathode of seawater dissolved oxygen battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776063A (en) * | 2019-10-22 | 2020-02-11 | 广州大学 | Carbon cathode material and preparation method and application thereof |
| CN111370646A (en) * | 2020-03-17 | 2020-07-03 | 青岛华高墨烯科技股份有限公司 | Preparation method of graphene hole cathode for seawater battery |
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| CN111370646A (en) * | 2020-03-17 | 2020-07-03 | 青岛华高墨烯科技股份有限公司 | Preparation method of graphene hole cathode for seawater battery |
| CN111370646B (en) * | 2020-03-17 | 2021-02-09 | 青岛华高墨烯科技股份有限公司 | Preparation method of graphene hole cathode for seawater battery |
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