CN107706446A - A kind of all solid lithium carbon dioxide secondary cell - Google Patents

A kind of all solid lithium carbon dioxide secondary cell Download PDF

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Publication number
CN107706446A
CN107706446A CN201710858214.6A CN201710858214A CN107706446A CN 107706446 A CN107706446 A CN 107706446A CN 201710858214 A CN201710858214 A CN 201710858214A CN 107706446 A CN107706446 A CN 107706446A
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China
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solid state
secondary cell
peg
composite gas
gas electrode
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CN201710858214.6A
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Inventor
陈军
李子凡
胡小飞
张雪静
陶占良
李海霞
于川茗
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Nankai University
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Nankai University
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A kind of all solid state Li CO2Secondary cell, assembled by negative electrode casing, shell fragment, pad, lithium piece, integrated composite gas electrode and porous anode shell, wherein lithium piece is negative pole, and integrated composite gas electrode is made up of all solid state inorganic organic polyelectrolyte, the conductive agent of surface coating loose structure and nickel foam or carbon paper；Shell fragment is stainless steel substrates, is filled for inside battery space to improve battery seal；Pad is stainless steel substrates；Integrated composite gas electrode is used to provide lithium ion, suppresses negative pole dendritic growth, avoids electrolyte volatilization and leakage.It is an advantage of the invention that：The solid state secondary battery does not contain liquid electrolyte, has the characteristics of big capacity, environment-friendly, inexpensive, long-life；Its preparation method is simple to operate, controllability is strong, uniformity is good, is advantageous to mass produce.

Description

A kind of all solid lithium-carbon dioxide secondary cell
Technical field
The present invention relates to a kind of novel secondary battery, particularly a kind of all solid lithium-carbon dioxide (Li-CO2) secondary electricity Pond and preparation method thereof, belong to mechanism of new electrochemical power sources field.
Background technology
In recent years, scientific worker and engineers continuously attempt to an industrial waste gas, dead flue gas, other carbon dioxide row Put the carbon dioxide (CO in facility2) store.Wherein, the most important storage mode of carbon dioxide is the physics by high pressure Environment, carbon dioxide is compressed into deep under ground to realize storage, or gaseous state CO2Compress into old oil field to produce oil The oil of field bottom.But this disposal options by carbon dioxide deep-burying underground be economically it is expensive, substantially completely according to A large amount of subsidies of international chlorenchyma and various countries' offer are provided.Therefore, how people's thinking uses carbon dioxide, will be this Industrial waste gas is transformed into commercial product and made a profit, rather than spends substantial contribution to be sealed in deep under ground.At present, titanium dioxide The catalysis oxidation industry of carbon, the base stock of all kinds of chemicals can be produced.Meanwhile can be with more environmentally friendly by discarded CO2Replace Crude oil is changed, so as to extract basic chemical industry raw material.Due to CO2It is a kind of stable molecule, such as utilizes CO2Need input energy, This is CO2The chemical problem that trans-utilization faces.
In CO2Electrochemical storage in terms of, people are in electrochemical reducing by CO2Generate CH4、C2H4, alcohol and acid, organic network The reduction of compound is fixed, optical electro-chemistry and electro-catalysis CO2, CO2Imitative photosynthesis and its electrochemical reduction etc. carried out exploration Research.In recent years, metal-gas cell turns into the study hotspot of chemical energy storage field of power supplies, with CO2For gas metal- Carbon dioxide battery is concerned by people because of many advantages, such as being easy to get with high-energy-density, high power density, positive active material, but It is limited to the selection of electrolyte component and additive, the design of gas electrode and selection of catalyst etc., metal-carbon dioxide battery All the time fail have great breakthrough.
The content of the invention
It is an object of the invention to problem be present for above-mentioned, there is provided a kind of all solid state Li-CO2Secondary cell, discharged Journey can be by CO2Carbon and lithium carbonate efficiently are reduced into, while discharges electric energy.Electrolyte is effectively inhibited using all solid state electrolyte Volatilization and leakage generation, improve battery security and stability.
The secondary cell has the characteristics of vast capacity, higher temperatures operation, environment-friendly, inexpensive and long-life.One Change gas electrode preparation method it is simple to operate, controllability is strong, uniformity is good, be advantageous to mass produce.
Technical scheme：
A kind of all solid state Li-CO2Secondary cell, its form are button battery.The button battery is by negative electrode casing, bullet Piece, pad, negative plate, integrated composite gas electrode and porous anode shell assemble.Wherein negative plate is metal lithium sheet, one Body composite gas electrode includes all solid state inorganic-organic polymer electrolyte and loads the nickel foam or carbon paper of CNT Collector, carbon dioxide are positive active material.Described all solid state inorganic-organic polymer electrolyte is poly- (metering system Acid esters) (PMA)/PEG (PEG-600)-LiClO4-SiO2Composite polymer electrolyte (CPE), positive conductive agent are more Wall carbon nano tube (CNT), collector are the nickel foam or carbon paper after roll-in.
The preparation method of the integrated composite gas electrode, comprises the following steps：
1) CNT (CNT) is scattered in 1-METHYLPYRROLIDONE (NMP) solution, and adds mass fraction 5%- 10% Kynoar (PVdF) is used as binding agent, and dispersion liquid is made.
2) the use of two pairs of rollers roll squeezer is nickel foam that 3mm nickel foams are rolled into that thickness is 0.8mm by thickness.
3) in the nickel foam or carbon cloth collector homogeneous dispersion made from step 1) being coated on after roll-in, it is placed in 120 DEG C of drying in oven, are made prefabricated positive pole.
4) use quality fraction is the 1-3% of methacrylate (MA) monomer azodiisobutyronitrile (AIBN) conduct Initiator, trigger MA polymerizations.Specific method is, by load weighted AIBN initiators, to be added in MA/PEG mixed solutions (weight Amount is than being 65:35) polymerisation is carried out at 65 DEG C 30 minutes, obtains poly- (methacrylate)/PEG mixture (PMA/PEG).Mass fraction is accounted for PMA/PEG 0-10% gas phase SiO2Nano particle is added to 1mL 1mol/L LiClO4 Acetone soln in, then keep be ultrasonically treated 1 hour.After being completely dissolved by supersound process, the solution is mixed with PMA/PEG Polymers mixes, and is then kept for 2 hours under mechanical agitation and ul-trasonic irradiation, obtains all solid state inorganic-organic hybrid polymer Electrolyte (CPE) solution.
5) all-solid-state composite polymer electrolyte (CPE) solution is repeated to cast on prefabricated positive pole.Cast for the first time CPE is penetrated into the loose structure of prefabricated positive pole, this will enable CNT be surrounded and therefore formed 3D electrode structures.The Second casting forms polymer dielectric film on positive pole, obtains integrated composite gas electrode.
6) by the polymer dielectric integration composite gas electrode of acquisition in an oven, dried 10 hours at 60 DEG C.
The all solid state Li-CO2The preparation method of secondary cell, its form are button battery.Comprise the following steps：
The preparation of button battery：Shell fragment, pad, lithium piece, integrated composite gas positive pole are sequentially placed into negative electrode casing, Then porous anode shell is installed, be finally compacted with sealing machine.The sealing machine pressure is 5-10MPa.
The technical Analysis of the present invention：
The all solid state Li-CO2Secondary cell, just extremely more wall carbon pipes and nickel foam of the compound high conductivity of solid electrolyte Or the integrated composite electrode that carbon paper collector is formed.All solid state electrolyte inhibits electrolyte to volatilize, and avoids leakage problem. Carbon material improves transmission of the ion in boundary, can effectively reduce cell interface impedance, lifts battery performance.
It is an advantage of the invention that：
The all solid state Li-CO2Secondary cell possesses operation, Large Copacity, circulation under high-energy-density, higher temperature (55 DEG C) The features such as long lifespan；All solid state electrolyte inhibits electrolyte to volatilize, and avoids leakage problem；Carbon material improves ion in phase The transmission at interface, cell interface impedance can be effectively reduced, improves battery performance.The button battery of preparation, which has, prepares letter Single, discharge and recharge overpotential is low (being less than 0.8V) after stabilization, the property for having extended cycle life and (cutting recyclable 100 circles of the mAh/g of capacity 1000) Energy.The present invention has important application value in energy storage and field of Environment Protection.
Brief description of the drawings
The all solid state Li-CO of Fig. 12Secondary cell schematic diagram.
Fig. 2 all solid state electrolyte ionic conductivities.
Fig. 3 SiO2Electrochemical impedance figure of addition when being 3wt%.
Fig. 4 aerosils TEM schemes.
Fig. 5 aerosil grain size distributions.
Fig. 6 all solid state electrolyte SEM front elevations.
Fig. 7 all solid state electrolyte SEM sectional drawings.
Fig. 8 all solid state electrolyte optical photographs.
Fig. 9 50mA/g electric currents, at room temperature button-shaped all solid state Li-CO2Secondary cell cycle performance curve.
The button-shaped all solid state Li-CO of Figure 102Secondary cell high rate performance.
Figure 11 is all solid state and liquid leakage comparison diagram.
The SEM figures (a) of 75 microns of thick electrolyte of Figure 12 and button-shaped all solid state Li-CO2Secondary cell cycle performance (b)。
The SEM figures (a) of 50 microns of thick electrolyte of Figure 13 and button-shaped all solid state Li-CO2Secondary cell cycle performance (b)。
The SEM figures (a) of 100 microns of thick electrolyte of Figure 14 and button-shaped all solid state Li-CO2Secondary cell cycle performance (b)。
Embodiment
With reference to specific embodiment, the present invention is further elaborated on.
Embodiment 1：
A kind of button-shaped all solid state Li-CO2Secondary cell, as shown in figure 1, by porous anode shell 1, integrated composite gas Electrode 2, lithium piece negative pole 3, pad 4, shell fragment 5, negative electrode casing 6 assemble.Integrated composite gas electrode is by conductive agent, afflux Body, polymer dielectric film composition, conductive agent is multi-walled carbon nanotube, and collector is nickel foam；The size of button cell is straight Footpath 20mm, thick 3.2mm, a diameter of 20mm of porous anode shell, uniform 19 a diameter of 1mm hole on porous anode shell；Shell fragment and Pad is stainless steel substrates.
(1) preparation of polymer film and integrated gas positive pole
By polymer average molecular weight be 600 business polyethylene glycol (PEG) and account for methyl acrylate (MA) monomer matter 1% AIBN initiator mixtures 8.145g of amount is added in 14.520g MA monomers.In 65 DEG C of stirring in water bath 0.5h, obtain PMA/PEG600 mixtures.By 1mol/L LiClO4, mass fraction account for PMA and PEG mass summation be 0,1,2,3,4,5,7, 10wt% (such as Fig. 2) gas phase SiO2Ultrasonic dissolution is in 50 ml acetone.Obtained acetone soln is added to PMA/PEG600 In mixture 1h is persistently stirred at 50 DEG C.Hereafter, drop to and be stored at room temperature 1h and obtain casting solution.
Business carbon nano tube 20mg is weighed in 120 DEG C of water removal 2h in vacuum drying oven.Dry CNT is scattered in Nmp solution, and active material slurry is made as binding agent in the PVdF for adding mass fraction 5%.Using two pairs of rollers roll squeezer by 3mm Thick nickel foam, roll-in are thick to 0.8mm.Active material slurry is applied to the foam nickel surface after roll-in, be made it is prefabricated just Pole.
Casting solution is poured in the load C NT paved in advance nickel foam (prefabricated positive pole) and carries out knifing.By what is scraped Film be placed in drying box 60 DEG C, 10h obtain integrated gas electrode.
Fig. 2 is PMA/PEG600/SiO2The electrical conductivity performance of all solid state electrolyte film, it can be seen that different quality containing SiO2Addition the ionic conductivity of all solid state film is had a significant impact, at 55 DEG C, 3wt% additions are optimal, reach 7.4 ×10-2mS cm-1.Fig. 3, which is illustrated, works as SiO2Electrochemical impedance figure of addition when being 3wt%, the polymer film equivalent resistance For 70 ohm.Optimal film is assembled for battery.Fig. 4 is that the TEM of nano silicon schemes, and display silica is amorphous State.Fig. 5 is the grain size distribution of nano silicon, and average grain diameter is less than 10nm.
Fig. 6 is all solid state film SEM front elevations.The figure shows that the surface of polymer dry film is substantially smooth, and its is coarse trickle Surface is advantageous to the close contact between electrode.Fig. 7 is all solid state film SEM sectional drawings, and the figure shows the thickness of polymer film For 75 μm.Fig. 8 is the optical photograph of all solid state electrolyte, is shown as that surface is smooth, and body phase is uniform, transparent.
(2) button-shaped all solid state Li-CO2The preparation of secondary cell
Shell fragment, pad, lithium piece, integrated composite gas electrode are sequentially placed into negative electrode casing, then porous anode is installed Shell, button-shaped all solid state Li-CO is finally assembled into 10MPa pressure compactions with sealing machine2Secondary cell, referring to Fig. 1.Battery Assembling process is carried out in the glove box full of Ar gas.
The button-shaped all solid state Li-CO that will be assembled2Secondary cell carries out charge-discharge test.Fig. 9 is all solid state Li-CO2Two Cycle performance curve of the primary cell under room temperature, 50mA/g electric currents, it can be seen that be pressed in 2.4V or so in first circle electric discharge, charge Middle pressure is 3.3V or so.2.2V is pressed in electric discharge in 100th week, pressure is 3.4V in charging.Figure 10 high rate performance, which is tested, to be shown, Under 50mA/g electric currents, occur pressing in electric discharge in 2.1V, pressing in charging occurs in 3.1V；In the case where current density is 100mA/g electric currents, Occur pressing in electric discharge in 1.9V, pressing in charging occurs in 3.1V.
Figure 11 illustrates all solid state Li-CO2The structural stability of battery, pass through the Li-CO with liquid electrolyte2Battery phase Leakage problem is not present than showing all solid state electrolyte.
Figure 12 is all solid state Li-CO of 75 μ m thick electrolyte2Cyclicity of the secondary cell under higher temperature (55 DEG C) Energy.Under 55 DEG C, 50mA/g electric currents, discharge and recharge is carried out by way of cutting capacity (1000mAh/g), is pressed in battery head Zhou Fang electricity 3.2V or so is pressed in 2.5V or so, charging.
Embodiment 2：
A kind of all solid state Li-CO2High temperature can run the preparation method of secondary cell, step and 1 basic phase of embodiment Together, difference is：The thickness of dielectric substrate is 50 μm.
Figure 13 is all solid state Li-CO that the dielectric film of 50 μ m-thicks assembles2Secondary cell, it is 1000 mAh/ cutting capacity G, the electrochemical data at 55 DEG C of operating temperature.Pressure is 2.4V or so in the electric discharge of battery first circle, and pressure is 3.2V or so in charging.50 The all solid state Li-CO of μ m-thick2Battery fails after the circle of circulation 30.
Comparison diagram 9 and Figure 13, it is therefore apparent that possess all solid state Li-CO of 75 μ m-thick electrolyte2The circulation of secondary cell is steady Qualitative to be greatly improved, discharge and recharge overpotential also greatly reduces.
Embodiment 3：
A kind of all solid state Li-CO2The preparation method of secondary cell, step is substantially the same manner as Example 1, difference It is：The thickness of dielectric substrate is 100 μm.
Figure 14 is all solid state Li-CO of 100 μ m thick electrolyte2The cycle performance of secondary cell.At 55 DEG C, 50mA/g Under electric current, discharge and recharge is carried out by way of cutting capacity (1000mAh/g), pressure is 2.2V or so in the electric discharge of battery first circle, is charged Middle pressure is 3.8V or so.It is 1.4V by pressure in 100 circle circulation electric discharges, pressure is 4.5V in charging.Comparison diagram 12 and Figure 14, show and It is clear to, all solid state Li-CO of 75 μ m-thick electrolyte2The cyclical stability of secondary cell is more preferable, and discharge and recharge overpotential is also lower.
It is an object of the invention to provide a kind of all solid state Li-CO based on all solid state electrolyte2Secondary cell storage bodies System, discharge process can be by CO2Carbon and lithium carbonate efficiently are reduced into, while discharges electric energy.The utilization of all solid state electrolyte is effective The generation of volatilization and the leakage of electrolyte is prevented, improves battery security and stability.The secondary cell have Large Copacity, Can be run under higher temperature (55 DEG C), environment-friendly, the inexpensive and long-life the characteristics of；Its preparation method is simple to operate, can Control property is strong, uniformity is good, is advantageous to mass produce, and is expected to turn into commercialized new battery system in the future.

Claims (6)

  1. A kind of 1. all solid state Li-CO that can be run at relatively high temperatures2Secondary cell, it is characterised in that：Successively by negative electrode casing, bullet The button cell that piece, pad, lithium piece, integrated composite gas electrode and porous anode shell assemble, wherein lithium piece are negative pole, Integrated composite gas electrode includes all solid state inorganic-organic polymer electrolyte and loads the nickel foam or carbon of CNT Paper collector, carbon dioxide are positive active material.
  2. 2. all solid state Li-CO according to claim 12Secondary cell, it is characterised in that：The integrated composite gas electrode In positive conductive agent be CNT；Collector is the nickel foam or carbon paper after roll-in；All solid state inorganic-organic polymer electricity Xie Zhiwei poly- (methacrylate) (PMA)/PEG (PEG-600)-LiClO4-SiO2Composite polymer electrolyte (CPE), polymer dielectric film thickness is respectively 50-150 μm.
  3. 3. all solid state Li-CO according to claim 12Secondary cell, it is characterised in that the size of the button cell is diameter 20mm, thick 3.2mm, a diameter of 20mm of porous anode shell, uniform 19 a diameter of 1mm hole on porous anode shell.
  4. 4. all solid state Li-CO according to claim 12Secondary cell, it is characterised in that all solid state inorganic-organic polymerization The preparation of thing electrolyte, comprises the following steps：
    Use quality fraction is used as initiator for the 1-3% of methyl acrylate (MA) monomer azodiisobutyronitrile (AIBN), draws Send out MA polymerizations；Specific method is load weighted AIBN initiators to be added in MA/PEG mixed solutions, MA and PEG weight Than for 65:Polymerisation is carried out at 35,65 DEG C 30 minutes, obtain poly- (methacrylate)/PEG mixture (PMA/ PEG)；Mass fraction is accounted for the 0-10% of PMA/PEG total amounts gas phase SiO2Nano particle is added to 1mL 1mol/L LiClO4 Acetone soln in, then keep be ultrasonically treated 1 hour, by be ultrasonically treated be completely dissolved after, the solution is mixed with PMA/PEG Polymers mixes, and is then kept under mechanical agitation and ul-trasonic irradiation 2 hours, finally, obtains all solid state inorganic-organic hybrid and gather Polymer electrolyte (CPE) solution.
  5. 5. all solid state Li-CO according to claim 12Secondary cell, it is characterised in that the system of integrated composite gas electrode It is standby, comprise the following steps：CNT (CNT) is scattered in 1-METHYLPYRROLIDONE (NMP) solution, and adds mass fraction 5%-10% Kynoar (PVdF) is used as binding agent, and dispersion liquid is made；The use of two pairs of rollers roll squeezer by thickness is 3mm foams Nickel is rolled into the nickel foam that thickness is 0.8mm；Obtained homogeneous dispersion is coated on to nickel foam or carbon paper collection after roll-in On fluid, 120 DEG C of drying in oven are placed in, prefabricated positive pole is made.By all-solid-state composite polymer electrolyte (CPE) solution weight Cast in again on prefabricated positive pole, then 60 DEG C of dryings 10 hours in an oven, obtain polymer dielectric integration composite gas Electrode.
  6. A kind of 6. all solid state Li-CO as claimed in claim 12The preparation method of secondary cell, it is characterised in that：By shell fragment, pad Piece, lithium piece, integrated composite gas electrode are sequentially placed into negative electrode casing, then install porous anode shell, finally with sealing machine with 5-10MPa pressure compactions.
CN201710858214.6A 2017-09-21 2017-09-21 A kind of all solid lithium carbon dioxide secondary cell Pending CN107706446A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109301403A (en) * 2018-10-11 2019-02-01 东北大学 A kind of metal-gas cell system
CN109616720A (en) * 2019-01-29 2019-04-12 东北大学 A kind of lithium carbon dioxide cell reaction device
CN110112512A (en) * 2019-04-19 2019-08-09 上海大学 Totally enclosed type metal-carbon dioxide battery and preparation method thereof
CN114784292A (en) * 2022-04-12 2022-07-22 西安交通大学 Lithium-carbon dioxide battery positive electrode material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN204391222U (en) * 2014-12-18 2015-06-10 北京立开源科技有限公司 A kind of coin shape zinc-air cell
CN105826638A (en) * 2016-05-23 2016-08-03 徐嘉陵 Zinc air battery electrode material and application thereof

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Publication number Priority date Publication date Assignee Title
CN204391222U (en) * 2014-12-18 2015-06-10 北京立开源科技有限公司 A kind of coin shape zinc-air cell
CN105826638A (en) * 2016-05-23 2016-08-03 徐嘉陵 Zinc air battery electrode material and application thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109301403A (en) * 2018-10-11 2019-02-01 东北大学 A kind of metal-gas cell system
CN109616720A (en) * 2019-01-29 2019-04-12 东北大学 A kind of lithium carbon dioxide cell reaction device
CN110112512A (en) * 2019-04-19 2019-08-09 上海大学 Totally enclosed type metal-carbon dioxide battery and preparation method thereof
CN110112512B (en) * 2019-04-19 2022-10-11 上海大学 Totally-enclosed metal-carbon dioxide battery and preparation method thereof
CN114784292A (en) * 2022-04-12 2022-07-22 西安交通大学 Lithium-carbon dioxide battery positive electrode material and preparation method thereof
CN114784292B (en) * 2022-04-12 2023-06-27 西安交通大学 Lithium-carbon dioxide battery positive electrode material and preparation method thereof

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Application publication date: 20180216