CN105633511B - A kind of Na-CO2Room temperature secondary cell and preparation method thereof - Google Patents
A kind of Na-CO2Room temperature secondary cell and preparation method thereof Download PDFInfo
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- CN105633511B CN105633511B CN201610211009.6A CN201610211009A CN105633511B CN 105633511 B CN105633511 B CN 105633511B CN 201610211009 A CN201610211009 A CN 201610211009A CN 105633511 B CN105633511 B CN 105633511B
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
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Abstract
A kind of Na CO2Room temperature secondary cell, the button cell assembled by negative electrode casing, shrapnel, gasket, sodium piece, diaphragm, electrolyte, carbon dioxide air electrode and porous anode shell, wherein sodium piece is cathode, carbon dioxide air electrode is anode, and carbon dioxide air electrode is made of the anode catalyst with porous structure with collector；Shrapnel is stainless steel substrates, is filled for inside battery space to improve battery seal；Gasket is stainless steel substrates；Diaphragm is between cathode sodium piece and plus plate current-collecting body, for obstructing electron-transport；Electrolyte is NaClO4/ tetraethyleneglycol dimethyl ether solution, electrolyte are infiltrated in diaphragm.It is an advantage of the invention that：The secondary cell have the characteristics that vast capacity, room temperature can fill, is environmental-friendly, is inexpensive, big multiplying power and long-life；Preparation method is easy to operate, controllability is strong, consistency is good, is conducive to mass produce.
Description
Technical field
The present invention relates to the preparation of novel Room Temperature secondary cell, especially a kind of Na-CO2Room temperature secondary cell and its preparation
Method.
Background technology
Since the industrial revolution, the strong greenhouse gases of the heat absorptivities such as carbon dioxide that the mankind are discharged into air increase year by year
Add, the greenhouse effects of air also enhance therewith, have caused the concern that a series of problems has caused whole world various countries.Therefore,
The capture of carbon dioxide and recycling cause people greatly to pay close attention to and pay attention to.Nowadays, consumer electronics, electric vehicle and intelligence electricity
The application scale in the fields such as net constantly expands, the higher energy-storage system of active demand energy density.Therefore, development higher energy is close
Degree, environmental-friendly, cheap novel battery are imperative.
Mainly by combustion of fossil fuel, photosynthesis of plant generates carbon dioxide.It is a kind of colorless and odorless under room temperature, does not help
Combustion, non-flammable gas, this makes it have good safety.But its high chemical stability also makes the reduction of carbon dioxide
Using very difficult.Novel Na-CO2Battery discharge procedure can efficiently reduce carbon dioxide to carbon, while discharge electric energy.It cuts
To currently, Na-CO2Battery has not been reported.
Invention content
It is an object of the invention to be directed to it is above-mentioned there are problems, a kind of Na-CO is provided2Room temperature secondary cell, the secondary electricity
Pond have the characteristics that vast capacity, room temperature can fill, is environmental-friendly, is inexpensive, big multiplying power and long-life；Preparation method operation letter
List, controllability is strong, consistency is good, and this method can effectively reduce the contact angle of active material and electrolyte, improves ion in phase boundary
The transmission in face can effectively reduce cell interface impedance, promote coulombic efficiency, be conducive to mass produce.
Technical scheme of the present invention：
A kind of Na-CO2Room temperature secondary cell, by negative electrode casing, shrapnel, gasket, sodium piece, diaphragm, electrolyte, carbon dioxide-
The button cell that air electrode and porous anode shell assemble, wherein sodium piece are cathode, and carbon dioxide-air electrode is just
Pole, carbon dioxide-air electrode are made of the anode catalyst with porous structure with collector；Shrapnel is stainless steel substrates, is used
It is filled in inside battery space to improve battery seal；Gasket is stainless steel substrates；Diaphragm is located at cathode sodium piece and anode collection
Between body, for obstructing electron-transport；Electrolyte is NaClO4/ tetraethyleneglycol dimethyl ether (TEGDME) solution, electrolyte infiltration
In diaphragm.
The anode catalyst is carbon nanotube, 60 ball alkene of carbon or reduction graphite；Collector is nickel foam, 400-1000
Purpose nickel screen or aluminium net, a diameter of 14mm of collector；Diaphragm is three layers that polyethylene-polypropylene-polyethylene is sequentially overlapped composition
Composite membrane (Celgard series membranes) or concrete dynamic modulus all-glass paper, wherein a diameter of 16mm of concrete dynamic modulus glass fiber filter paper are thick
Degree is 0.3mm, porosity 92-98%；NaClO4A concentration of 1mol L of/tetraethyleneglycol dimethyl ether (TEGDME) solution-1；
The size of button cell is diameter 20mm, thickness 3.2mm, a diameter of 20mm of porous anode shell, uniformly distributed diameter on porous anode shell
For 19 holes of 1mm.
The preparation method of the carbon dioxide-air electrode, includes the following steps：
1) carbon nanotube, 60 ball alkene of carbon or reduction graphite is 2 hours dry at 120 DEG C, -0.1Mpa；
2) carbon nanotube, 60 ball alkene of carbon or the reduction graphite after drying are mixed with tetraethyleneglycol dimethyl ether (TEGDME),
The anode catalyst of porous structure is made in the ultrasonic reaction 30min at 40KHz；
3) Kynoar (PVdF) is added in the anode catalyst-TEGDME dispersion liquids of porous structure as anode
The binder of catalyst and collector, the additive amount of vinylidene are the 5% of dispersion liquid quality, and dispersion liquid is then sprayed on temperature
On the collector of 300-600 DEG C of degree, the amount ratio of the anode catalyst of porous structure and TEGDME are 20mg in dispersion liquid：
Carbon dioxide-air electrode is made in 10mL.
A kind of Na-CO2Shrapnel, gasket, sodium piece, diaphragm are sequentially placed into negative by the preparation method of room temperature secondary cell
In the shell of pole, 30 μ L electrolyte are added dropwise, place the carbon dioxide-air electrode prepared, then porous anode shell is installed, finally used
Sealing machine is with 5MPa pressure compactions.
The technology analysis of the present invention：
The Na-CO2Room temperature anode of secondary battery is the semi-open battery of carbon dioxide-air electrode, and air electrode is tool
The battery device being made of with collector the anode catalyst of porous structure, effect is to provide diffusion admittance for carbon dioxide,
And provide active site for the discharging product sodium carbonate generated in discharge process.Pass through in the preparation of binder free air electrode
Previously prepared catalyst dispersion atomizing spraying is formed on the porous current collector that temperature is 300-600 DEG C.
By the total differential to basic Thermodynamics Formulas it is found that the raising collection liquid surface tension with temperature reduces.
Catalyst when collector low surface tension in attachment can have and the stronger binding force of collector when it restores room temperature.
This method is avoided active material being made thin using binder and is uniformly supported on porous current collector.And it is easy to operate, can
Control property is strong, consistency is good.
The present invention provides Na-CO2The surface modification side of carbon-based material used in air electrode catalyst in battery
Method, this method can effectively reduce the contact angle of active material and electrolyte, improve ion in the transmission of boundary, can effectively drop
Low cell interface impedance promotes coulombic efficiency.
It is an advantage of the invention that：
The Na-CO2Room temperature secondary cell, which can be restored efficiently, has high energy density, room temperature using atmospheric carbon dioxide
Can fill, large capacity, the features such as having extended cycle life；The present invention provides the anode catalyst preparations suitable for Semi-open system battery
Method, this method is simple and easy to do, can make active material uniform fold collection liquid surface, improve the utilization rate of catalyst；This hair
It is bright to provide for Na-CO2The modified modified method in surface of anode carbon material catalyst, by being reacted with electrolyte,
It makes it have smaller contact angle, preferably infiltrate electrolyte, improve transmission of the ion in boundary.The button of designed making
Formula battery has reversible specific capacity height (60000mAh g-1), it is low (＜ 3.7V) to fill a current potential, good rate capability (4A g-1Shi You
4000mAh g-1), it has extended cycle life (by capacity 2000mAh g-1Available 200 circle cycle) performance.The Na-CO2It is secondary
Battery have room temperature can fill, large capacity (1100Wh kg-1), low overpotential (0.6V), big multiplying power (4A g-1When have 4000mAh
g-1Reversible capacity) and the characteristics of the long-life (by capacity 2000mAh g-1Available 200 circle cycle).The present invention is in energy storage
With in field of environment protection all have important application value.
Description of the drawings
Fig. 1 is Na-CO2Battery air electrode carbon nanotube SEM.
Fig. 2 is Na-CO2Battery air electrode, collector load carbon nanotube side SEM.
Fig. 3 is the ionic conductivity of different electrolyte.
Fig. 4 is that the battery impedance after different condition surface treatment is carried out to carbon nanotube.
Fig. 5 is the contact angle of carbon nanotube and carbon pipe and TEGDME of the EtOH Sonicate after 2 hours.
Fig. 6 is the contact angle of carbon nanotube and the carbon nanotube and TEGDME of TEGDME ultrasounds after five minutes.
Fig. 7 is the contact angle of carbon nanotube and TEGDME of the carbon nanotube with TEGDME after 2 hours ultrasonic.
Fig. 8 is battery system 1M NaClO4/ TEGMDE voltage windows (Ar atmosphere encloses middle test).
Fig. 9 is to carry out surface modification to carbon nanotube by TEGDME, does not add the charge and discharge electrograph of binder.
Figure 10 is to carry out surface modification to carbon nanotube by TEGDME, adds the charge and discharge electrograph of 5wt% binders.
Figure 11 is to carry out surface modification to carbon nanotube by TEGDME, does not add the charge and discharge electrograph of binder.
Figure 12 is reduced graphene as Na-CO2The charge and discharge electrograph of anode catalyst.
Figure 13 is 60 ball alkene of carbon as Na-CO2The charge and discharge electrograph of anode catalyst.
Figure 14 is interception capacity 1000mAh g-1Charge and discharge electrograph.
Figure 15 is interception capacity 2000mAh g-1Charge and discharge electrograph.
Figure 16 is Na-CO2Battery high rate performance.
Figure 17 is charge and discharge electrode slice XRD characterization, detects discharging product sodium carbonate.
Figure 18 is charge and discharge Raman characterization, verifies discharging product sodium carbonate and carbon.
Figure 19 is the influence for excluding the carbon that carbon material electrode generates detection battery discharge, and Na- is assembled by nano silver wire
CO2Anode detects discharging product carbon by electrical losses power spectrum (EELS).
Figure 20 is the precipitation test of carbon dioxide in charging process.
Figure 21 is Na-CO2Secondary room temperature battery structure schematic diagram.
In figure：1. negative electrode casing, 2. shrapnels, 3. gaskets, 4. sodium pieces, 5. diaphragms, 6. anode catalyst, 7. collector, more than 8.
Hole anode cover.
Specific implementation mode
With reference to specific embodiment, it is further elaborated on the present invention.
Embodiment 1：
A kind of Na-CO2Room temperature secondary cell, as shown in figure 21, by negative electrode casing 1, shrapnel 2, gasket 3, sodium piece 4, diaphragm 5,
The button cell that electrolyte, carbon dioxide-air electrode and porous anode shell 8 assemble, wherein sodium piece 4 are cathode, dioxy
It is anode to change carbon-air electrode, and carbon dioxide-air electrode is by 7 groups of anode catalyst 6 and collector with porous structure
At；Shrapnel 2 is stainless steel substrates, is filled for inside battery space to improve battery seal；Gasket 3 is stainless steel substrates；Diaphragm 5
Between cathode sodium piece 4 and plus plate current-collecting body 7, for obstructing electron-transport；Electrolyte is NaClO4/ tetraethyleneglycol dimethyl ether
(TEGDME) solution, electrolyte are infiltrated in diaphragm 5；The anode catalyst is 6 carbon nanotubes；Collector 7 is 400 purposes
Nickel screen, a diameter of 14mm of collector；Diaphragm 5 be concrete dynamic modulus all-glass paper, a diameter of 16mm of concrete dynamic modulus glass fiber filter paper,
Thickness is 0.3mm, porosity 92-98%；NaClO4A concentration of 1mol L of/tetraethyleneglycol dimethyl ether (TEGDME) solution-1；
The size of button cell is diameter 20mm, thickness 3.2mm, a diameter of 20mm of porous anode shell 8, on porous anode shell it is uniformly distributed directly
Diameter is 19 holes of 1mm.
A kind of Na-CO2The preparation method of room temperature secondary cell, steps are as follows：
1) screening of electrolyte
Common electrochemically stable electrolyte includes DMSO, TEGDME and DME.Wherein DMSO and Na metal reactions, show
So unsuitable Na-CO2Battery；And TEGDME (275 DEG C) has higher boiling point compared with DME (85 DEG C), volatility is lower,
It is more suitable for Na-CO2Open battery system.Then, it is solvent, NaClO that we, which test TEGDME,4It is solute with NaTFSI
The ionic conductivity of two kinds of electrolyte in figure as shown in figure 3, show：NaClO4/TEGDME has higher ionic conductivity
(0.178S m-1), then it is chosen to be final electrolyte.It is with wide voltage window (1.2V -4.5V).
2) preparation of the anode catalyst of porous structure
It weighs business carbon nano tube 20mg to dry 2 hours in 120 DEG C in vacuum drying oven, under -0.1Mpa, then will be dry
Carbon pipe, which is put into multiply, to be had in the beaker of 20mLTEGDME, the ultrasonic reaction 30min at 40KHz, and the anode catalytic of porous structure is made
Agent.
Fig. 4 is that the battery impedance after different condition surface treatment is carried out to carbon nanotube.Show in figure：Use TEGDME
Carbon nanotube of the ultrasound after 2 hours has highest conductivity.
Fig. 5 is the contact angle of carbon nanotube and carbon pipe and TEGDME of the EtOH Sonicate after 2 hours.Show in figure：With ethyl alcohol
The contact angle that carbon pipe of the ultrasound after 2 hours is 18.1 ° with TEGDME, possesses relatively general contact angle.
Fig. 6 is the contact angle of carbon nanotube and the carbon nanotube and TEGDME of TEGDME ultrasounds after five minutes.Show in figure：
The contact angle for being 18.0 ° with the carbon pipe of TEGDME ultrasounds after five minutes and TEGDME, possesses relatively good contact angle.
Fig. 7 is the contact angle of carbon nanotube and TEGDME of the carbon nanotube with TEGDME after 2 hours ultrasonic.Show in figure：
The contact angle for being 13.8 ° with TEGDME with carbon pipes of the TEGDME after 2 hours ultrasonic, possesses relatively optimal contact angle.
3) preparation of carbon dioxide-air electrode
Kynoar (PVdF) is added in the anode catalyst-TEGDME dispersion liquids of porous structure is used as anode catalytic
The binder of agent and collector, the additive amount of vinylidene are the 5% of dispersion liquid quality, and dispersion liquid is then sprayed on temperature
400 DEG C, on the collectors of 400 mesh, the amount ratio of the anode catalyst of porous structure and TEGDME are 20mg in dispersion liquid：
10mL, carbon nanotube are attached to nickel screen surface by molecular separating force, and carbon dioxide-air electrode that load capacity is 5 μ g is made.
Fig. 1 is Na-CO2Battery air electrode carbon nanotube SEM.Show in figure：Carbon nanotube anode catalyst has rich
Rich accumulation hole and Large ratio surface is conducive to discharging product and grows.
Fig. 2 is Na-CO2Battery air electrode, collector load carbon nanotube side SEM.Show in figure：Carbon tube layer is with big
About 0.5 micron in homogeneous thickness is supported on collection liquid surface.
Figure 10 is to carry out surface modification to carbon nanotube by TEGDME, adds the charge and discharge electrograph of 5wt% binders.Figure 11
To carry out surface modification to carbon nanotube by TEGDME, the charge and discharge electrograph of binder is not added.Comparison diagram 10 is visible with Figure 11：
There is discharge platform in 1.6V or so in first week, and 2.8V starts charging platform occur.Since the addition of binder sodium phenol makes battery
Resistance increases, low 0.7V when its discharge voltage being caused less to add binder.
4)Na-CO2The preparation of room temperature secondary cell
Shrapnel, gasket, sodium piece, diaphragm are sequentially placed into negative electrode casing, 30 μ L electrolyte are added dropwise, place the dioxy prepared
Change carbon-air electrode, then porous anode shell is installed, finally uses sealing machine with 5MPa pressure compactions.Cell assembling processes exist
It is carried out in glove box full of Ar gas.
Na-CO2The charge-discharge test of room temperature secondary cell
Test voltage ranging from 1.5-4.0V.
Fig. 8 is battery system 1M NaClO4/ TEGMDE voltage windows (Ar atmosphere encloses middle test).Show in figure：
It is electrochemically stable that TEGDME electrolytes, which tie up to 1V to 4.5V,.
Fig. 9 is button Na-CO2Battery is in 1A g-1Under electric current, 500mAh g are intercepted-1Charging and discharging curve.It can be with from figure line
Find out, first week discharge platform occurs in 2.3V, and charging platform occurs in 3.2V.It is 4Ag in current density-1Under obtain 4000mAh g-1Specific capacity (voltage ＞ 2V).
Embodiment 2：
A kind of Na-CO2The preparation method of room temperature secondary cell, step is substantially the same manner as Example 1, and difference exists
In：Replace carbon nanotube with graphene.
Figure 12 is Na-CO2Battery is in 1Ag-1Under electric current, 500mAh g are intercepted-1Charging and discharging curve.It can from figure line
Go out, first week discharge platform occurs in 2.2V or so, and charging platform occurs in 3.1V.
Embodiment 3：
A kind of Na-CO2The preparation method of room temperature secondary cell, step is substantially the same manner as Example 1, and difference exists
In：Replace carbon nanotube with 60 ball alkene of carbon.
Figure 13 is button Na-CO2Battery is in 1Ag-1Under electric current, 500mAh g are intercepted-1Charging and discharging curve.It can be with from figure line
Find out, first week discharge platform occurs in 1.4V or so, and charging platform occurs in 3.5V.
Na-CO2Battery is a kind of completely new energy storage system, the quality Na-CO based on active material2Battery possesses
12000Wh kg-1Power density.Quality Na-CO based on carbon dioxide and sodium2Battery has 1100Wh kg-1Theoretical work(
Rate density.The theoretical energy density of nearly 3 times of lithium ion batteries.(Bruce,P.G.； Freunberger,S.A.；
Hardwick,L.J.；Tarascon,J.-M.,Li–O2and Li–S batteries with high energy
storage.Nature Materials 2011,11(1),19-29.)
Na-CO2The detection of room temperature secondary cell：
Figure 14 is using blue electrical measurement test system (Wuhan) to button Na-CO2Battery carries out 1000 mAh g of interception capacity-1's
Constant current charge-discharge test figure.Show in figure：In interception specific capacity 1000mAh g-1When, Na-CO2Battery can stablize cycle 200
Period.In button Na-CO2Before battery in 200 circle cycles, discharge voltage is more than 2V, and charging voltage is less than 4V, in electrolyte
Within the scope of voltage window.
Figure 15 is using blue electrical measurement test system (Wuhan) to button Na-CO2Battery carries out 2000 mAh g of interception capacity-1's
Constant current charge-discharge test figure.Show in figure：In interception specific capacity 2000mAh g-1When, Na-CO2Battery can stablize cycle 200
Period.In preceding 200 circle cycle, discharge voltage is more than 2V, and charging voltage is less than 4V, in the voltage window range of electrolyte
It is interior.
Figure 16 is using blue electrical measurement test system (Wuhan) to button Na-CO2Battery carries out 2000 mAh g of interception capacity-1's
Constant current charge-discharge test figure.Show in figure：It is 1Ag in charging and discharging currents density-1To 4Ag-1When, battery charging and discharging overpotential has
Increased, but discharge voltage is more than 2V, charging voltage is less than 4V, within the scope of the voltage window of electrolyte.
Figure 17 is charge and discharge electrode slice XRD characterization, detects discharging product sodium carbonate.Show in figure：By to discharging product
X-ray diffraction analysis, obtain the diffracted signal of sodium carbonate.Prove Na-CO2Battery produces sodium carbonate in discharge process,
Demonstrate the cell reaction
Figure 18 is the influence for excluding the carbon that carbon material electrode generates detection battery discharge, and Na-CO is assembled by nano silver wire2Electricity
Pond anode.Show in figure：By the Raman spectrum analysis to discharging product, the Raman signal of sodium carbonate and carbon is obtained.Demonstrate Na-
CO2Battery produces sodium carbonate and carbon in discharge process, demonstrates the cell reaction
Figure 19 is the influence for excluding the carbon that carbon material electrode generates detection battery discharge, and Na- is assembled by nano silver wire
CO2Anode detects discharging product carbon by electrical losses power spectrum (EELS).Show in figure： Na-CO2Battery is discharging
Carbon is produced in the process, demonstrates the cell reaction
Figure 20 is the precipitation test of carbon dioxide in charging process.Show in figure：In battery charging process, carbon dioxide
Production quantity, with according toThe calculated theoretical production quantity of stoichiometric number is consistent.Final card
The real cell reaction.
The purpose of the present invention is to provide it is a kind of it is novel, room temperature is reversible, the energy storage system of vast capacity, energy source is in disappearing
Consume GHG carbon dioxide.The energy storage system is preserved the ecological environment while meeting people's energy demand, is realized sustainable
Development.The secondary cell have the characteristics that vast capacity, room temperature can fill, is environmental-friendly, is inexpensive, big multiplying power and long-life.It is special
Not, it is noted that at present it has been reported that lithium ion battery compared with, battery system of the invention has preparation method convenient, former
Material derives from a wealth of sources, of low cost.The present invention can be widely used in power battery and extensive energy storage field.Due to energy of the present invention
It is enough efficiently to utilize GHG carbon dioxide.Therefore, in energy storage with environmentally friendly two fields, it all applies valence with great
Value is expected to become commercialized new battery system in the future.
Claims (4)
1. a kind of Na-CO2Room temperature secondary cell, it is characterised in that：By negative electrode casing, shrapnel, gasket, sodium piece, diaphragm, electrolyte, two
The button cell that carbonoxide-air electrode and porous anode shell assemble, wherein sodium piece are cathode, carbon dioxide-air electricity
Extremely positive, carbon dioxide-air electrode is made of anode catalyst and collector, and anode catalyst all has more with collector
Pore structure；Shrapnel is stainless steel substrates, is filled for inside battery space to improve battery seal；Gasket is stainless steel substrates；Every
Film is between cathode sodium piece and plus plate current-collecting body, for obstructing electron-transport；Electrolyte is NaClO4/ tetraethyleneglycol dimethyl ether
(TEGDME) solution, electrolyte are infiltrated in diaphragm.
2. Na-CO according to claim 12Room temperature secondary cell, it is characterised in that：The anode catalyst be carbon nanotube,
60 ball alkene of carbon or reduction graphite；Collector is nickel foam, the nickel screen of 400-1000 mesh or aluminium net, a diameter of 14mm of collector；Every
Film is the sandwich diaphragm or concrete dynamic modulus all-glass paper that polyethylene-polypropylene-polyethylene is sequentially overlapped composition, wherein concrete dynamic modulus
A diameter of 16mm of all-glass paper, thickness 0.3mm, porosity 92-98%；NaClO4/ tetraethyleneglycol dimethyl ether
(TEGDME) a concentration of 1molL of solution-1；The size of button cell is diameter 20mm, thickness 3.2mm, the diameter of porous anode shell
For 20mm, 19 holes of uniformly distributed a diameter of 1mm on porous anode shell.
3. Na-CO according to claim 12Room temperature secondary cell, it is characterised in that：The system of the carbon dioxide-air electrode
Preparation Method includes the following steps：
1) carbon nanotube, 60 ball alkene of carbon or reduction graphite is 2 hours dry at 120 DEG C, -0.1Mpa；
2) carbon nanotube, 60 ball alkene of carbon or the reduction graphite after drying are mixed with tetraethyleneglycol dimethyl ether (TEGDME),
Anode catalyst-TEGDME the dispersion liquids of porous structure are made in ultrasonic reaction 30min under 40KHz；
3) binder of the addition as anode catalyst and collector in the anode catalyst-TEGDME dispersion liquids of porous structure
Kynoar (PVdF), the additive amount of Kynoar is the 5% of dispersion liquid quality, and dispersion liquid is then sprayed on temperature
On 300-600 DEG C of collector, the amount ratio of the anode catalyst of porous structure and TEGDME are 20mg in dispersion liquid：10mL,
Carbon dioxide-air electrode is made.
4. a kind of Na-CO as described in claim 12The preparation method of room temperature secondary cell, it is characterised in that：By shrapnel, gasket,
Sodium piece, diaphragm are sequentially placed into negative electrode casing, and 30 μ L electrolyte are added dropwise, places the carbon dioxide-air electrode prepared, then pacifies
Porous anode shell is filled, finally uses sealing machine with 5MPa pressure compactions.
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| CN106099261A (en) * | 2016-07-18 | 2016-11-09 | 南开大学 | A kind of quasi-solid-state button Na CO2room temperature secondary cell and preparation method thereof |
| CN106207318A (en) * | 2016-07-18 | 2016-12-07 | 南开大学 | A kind of quasi-solid-state Soft Roll formula Na CO2room temperature secondary cell and preparation method |
| CN106450514B (en) * | 2016-11-11 | 2019-03-26 | 南开大学 | A kind of quasi- solid state N a-CO2Secondary cell and preparation method thereof |
| CN107681161A (en) * | 2017-09-21 | 2018-02-09 | 南开大学 | A kind of all solid state Soft Roll formula lithium carbon dioxide secondary cell and preparation method thereof |
| CN110534778B (en) * | 2019-08-30 | 2020-08-14 | 中南大学 | Organic positive electrode for sodium-carbon dioxide battery, preparation method of organic positive electrode and sodium-carbon dioxide battery |
| CN111082161B (en) * | 2020-01-06 | 2021-11-26 | 中南大学 | Mixed system sodium-carbon dioxide secondary battery and preparation method thereof |
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| CN102934279A (en) * | 2010-06-08 | 2013-02-13 | 雷蒙特亚特特拉维夫大学有限公司 | Rechargeable alkali metal-air battery |
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