CN107681161A - A kind of all solid state Soft Roll formula lithium carbon dioxide secondary cell and preparation method thereof - Google Patents

A kind of all solid state Soft Roll formula lithium carbon dioxide secondary cell and preparation method thereof Download PDF

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CN107681161A
CN107681161A CN201710858170.7A CN201710858170A CN107681161A CN 107681161 A CN107681161 A CN 107681161A CN 201710858170 A CN201710858170 A CN 201710858170A CN 107681161 A CN107681161 A CN 107681161A
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solid state
secondary cell
peg
positive pole
composite
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陈军
李子凡
孙建超
胡小飞
杨浩
陶占良
李海霞
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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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • 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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Abstract

A kind of all solid state Soft Roll formula Li CO2High temperature can run secondary cell, and its form is Soft Roll formula battery.The soft-package battery is made up of negative plate, composite integrated positive pole and plastic foil outer packing.Wherein negative plate is metal lithium sheet, just extremely poly- (methacrylate) (PMA)/PEG (PEG 600) LiClO of composite integrated4‑SiO2Composite polymer electrolyte (CPE) and multi-walled carbon nanotube (CNT), collector are the nickel foam after roll-in.Composite polymeric film is all solid state electrolyte, avoids the volatilization and leakage of electrolyte, for providing lithium ion, suppressing cathode of lithium dendritic growth.The secondary cell have Large Copacity, can higher temperature run, environment-friendly, the inexpensive and long-life the characteristics of.Its preparation method is simple to operate, controllability is strong, uniformity is good, is advantageous to mass produce.

Description

A kind of all solid state Soft Roll formula lithium-carbon dioxide secondary cell and preparation method thereof
Technical field
The present invention relates to a kind of novel secondary battery, particularly a kind of all solid state Soft Roll formula lithium-carbon dioxide (Li-CO2) Secondary cell 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 will use carbon dioxide, by this Kind 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, dioxy Change 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 CO2 Crude oil is replaced, so as to extract basic chemical industry raw material.Due to CO2It is a kind of stable molecule, such as utilizes CO2Need input energy Amount, 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 spy Research without hesitation.In recent years, metal-gas cell turns into the study hotspot of chemical energy storage field of power supplies, with CO2For the gold of gas Category-carbon dioxide battery is closed because of many advantages, such as being easy to get with high-energy-density, high power density, positive active material by people Note, but it is limited to the selection of electrolyte component and additive, the design of gas electrode and selection of catalyst etc., metal-titanium dioxide Carbon battery fails have great breakthrough all the time.
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 Soft Roll formula Li-CO2Secondary cell and Its preparation method.The discharge process of secondary cell can be by CO2Carbon and lithium carbonate efficiently are reduced into, while discharges electric energy.Utilize All solid state electrolyte effectively inhibits the generation of volatilization and the leakage of electrolyte, improves battery security and stability.This two Primary cell have vast capacity, can higher temperature run, environment-friendly, the inexpensive and long-life the characteristics of.Its 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 Soft Roll formula Li-CO2Secondary cell, its form are Soft Roll formula battery.The soft-package battery by negative plate, Composite integrated positive pole and plastic foil outer packing composition.Wherein negative plate is metal lithium sheet, and composite integrated positive pole includes complete solid State inorganic-organic polymer composite membrane electrolyte and the foamed nickel current collector for being loaded with CNT.The composite membrane of polymer electricity Xie Zhiwei poly- (methacrylate) (PMA)/PEG (PEG-600)-LiClO4-SiO2Composite polymer electrolyte (CPE), composite membrane of polymer Electrolyte film thickness is 50-150 μm, and positive conductive agent is multi-walled carbon nanotube (CNT), collector For the nickel foam after roll-in.
The preparation method of the integrated positive pole, comprises the following steps：
1) preparation of dispersion liquid：CNT (CNT) is scattered in 1-METHYLPYRROLIDONE (NMP) solution, and adds matter Amount fraction 5%-10% Kynoar (PVdF) is used as binding agent.
2) the use of two pairs of rollers roll squeezer is that 3mm nickel foams are rolled into the nickel foam that thickness is 0.8mm and are used as afflux using thickness Body.
3) by above-mentioned steps 1) prepare homogeneous dispersion be coated on roll-in after foamed nickel current collector on.It is placed in 120 DEG C drying in oven, is 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 the gas phase SiO of PMA/PEG total amounts 0-10% (being preferably 3%)2Nano particle is added to 1mol/L LiClO4Acetone soln in, then keep be ultrasonically treated 1 hour.It is after being completely dissolved by supersound process, this is molten Liquid mixes polymers with PMA/PEG and mixed, and is then kept for 2 hours under mechanical agitation and ul-trasonic irradiation, obtains all solid state compound poly- Polymer electrolyte (CPE) solution.
5) all-solid-state composite polymer electrolyte (CPE) solution is repeated to cast on prefabricated positive pole, obtains polymer Electrolyte integration positive pole.For the first time casting CPE is penetrated into the loose structure of prefabricated positive pole, this will enable CNT by Surround and therefore form 3D electrode structures.Cast in for the second time and polymer dielectric film is formed on positive pole.
6) the polymer dielectric integration positive pole of acquisition is put into baking oven and dried 10 hours at 60 DEG C.
The all solid state Soft Roll formula Li-CO2The preparation method of secondary cell.Comprise the following steps：
It is prepared by Soft Roll formula battery：In the glove box full of argon gas, lithium piece is flattened and is placed in composite integrated positive pole Electrolyte side, battery core is formed by overlapped way, then inserted in aluminum-plastic composite membrane shell, and encapsulate sealing.Soft-package battery Size be length of side 200mm, thick 2mm.
The technical Analysis of the present invention：
The all solid state Soft Roll formula Li-CO2Secondary cell, pass through more wall carbon pipes and the bubble of the compound high conductivity of solid electrolyte Foam nickel set fluid, form the battery device for including integrated positive pole.All solid state electrolyte does not have electrolyte volatilization, it is therefore prevented that 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 Soft Roll formula Li-CO2Secondary cell possesses high-energy-density, can hot operation, Large Copacity, cycle life The features such as long；All solid state electrolyte fundamentally solves electrolyte volatilization, it is therefore prevented that leakage problem；Carbon material improves ion In the transmission of boundary, cell interface impedance can be effectively reduced, improves battery performance.The soft-package battery performance of assembling is informed against Enclose 521Wh kg-1High-energy-density, and recyclable 440 hours, 100 circles.The present invention has in energy storage and field of Environment Protection Important application value.
Brief description of the drawings
The all solid state Li-CO of Fig. 12Soft-package battery schematic diagram.
The optical photograph of nickel foam after Fig. 2 roll-ins.
The SEM figures of Fig. 3 CNTs.
Coated polymeric figure on Fig. 4 coating machines.
AFM (AFM) figure of Fig. 5 full solid state polymer electrolytes.
The AFM Young's modulus figures of Fig. 6 full solid state polymer electrolytes.
Fig. 7 full solid state polymer electrolyte Young's modulus distribution maps.
Fig. 8 full solid state polymer electrolyte roughness distribution maps.
Fig. 9 Li-CO2In-situ Raman figure corresponding to first charge-discharge.
55 DEG C of Figure 10, the charging and discharging curve under 5mA electric currents.
The all solid state Li-CO of Figure 112Soft-package battery cycle performance figure.
Figure 12 bends 180 ° of all solid state Li-CO2Soft-package battery cycle performance.
Figure 13 winds 360 ° of all solid state Li-CO2Soft-package battery cycle performance.
Embodiment
With reference to specific embodiment, the present invention is further elaborated on.
Embodiment 1：
A kind of all solid state Soft Roll formula Li-CO2Secondary cell, as shown in figure 1, the soft-package battery includes plastic foil outer packing 5th, lithium anode 4, polymer dielectric film 3, carbon nano-tube catalyst 2 and foamed nickel current collector 1, dielectric film 3, carbon nanometer Pipe catalyst 2 and foamed nickel current collector 1 form composite integrated positive pole, and polymer dielectric film is poly- (methacrylate) (PMA)/PEG (PEG-600)-LiClO4- 3wt%SiO2, polymer dielectric film thickness is 75 μm.Outer packing plastic 5 covering negative sides, for protect cathode of lithium not with the carbon dioxide exposure in atmosphere.
(1) preparation of composite integrated 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 the gas phase SiO that mass fraction accounts for PMA with PEG mass summation is 0-10 wt%2Ultrasonic dissolution exists 50ml 1mol/L LiClO4Acetone soln in.Obtained acetone soln is added in PMA/PEG600 mixtures 50 DEG C Persistently stir 1h down.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 10%.Will using two pairs of rollers roll squeezer Nickel foam thick 3mm, roll-in are thick to 0.8mm.Active material slurry is applied to the foam nickel surface after roll-in, is made prefabricated Positive pole.
Casting solution is poured in the load C NT paved in advance nickel foam (prefabricated positive pole) and carries out knifing, 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.The dielectric substrate thickness finally given after drying is 75 μm.It will scrape Film be placed in drying box 60 DEG C, 10h obtain all solid state Li-CO2Composite integrated positive pole.
Fig. 2 is the optical photograph of nickel foam after roll-in, and nickel foam has good pliability after roll-in.
Fig. 3 is the high power transmission electron microscope photo of carbon nano-tube catalyst, it can be seen that used CNT CNT feature interplanar distance with 0.34nm.Fig. 4 illustrates integrated preparation process, using coating machine pre-prepared Knifing on positive pole (nickel foam after the roll-in of load CNT), prepares polymer dielectric.Fig. 5 is polymer dielectric AFM (AFM) figure of film, display bath surface are smooth.Fig. 6 is the atom of polymer electrolyte film Force microscope Young's modulus figure, polymer dielectric have stronger mechanical strength.Fig. 7 is the Young's modulus of polymer dielectric Distribution, shows that polymer dielectric surface mechanical strength is evenly distributed.Fig. 8 is that the roughness of polymer electrolyte film is distributed, Show that bath surface is coarse to be evenly distributed.
(2) flexible all solid state Soft Roll formula Li-CO2The preparation of secondary cell
Lithium piece is flattened to the electrolyte side for being placed in composite integrated positive pole, battery core is formed by overlapped way, then put Enter in aluminum-plastic composite membrane shell, and encapsulate sealing.Cell assembling processes are carried out in the glove box full of Ar gas.
Fig. 9 is all solid state Soft Roll formula Li-CO of on-line checking2The Raman signal of positive pole in charge and discharge process, the results showed that Li-CO2Battery, along with the generation and disappearance of lithium carbonate, shows Li-CO in charge and discharge process2The discharging product of battery includes Lithium carbonate.
The all solid state Soft Roll formula Li-CO that will be assembled2Secondary cell is placed in formation state, carries out charge-discharge test.Figure 10 It is the charge-discharge performance at 55 DEG C for test temperature, the discharge capacity under 5mA electric currents is 993.3mAh, and about 2.4V is pressed in electric discharge, Based on integral battery door quality 4.38g (wherein comprising 3.30g composite integrateds positive pole, 0.40g lithium anodes, 0.68g plastic-aluminums Film), energy density is equivalent to 521Wh kg-1.Higher than the theoretical energy density of lithium ion battery.
Figure 11 illustrates the cycle performance of soft-package battery, and 2.4V or so is pressed in electric discharge, 3.5V or so is pressed in charging, can Enclosed with stable circulation 100.
Embodiment 2：
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：By all solid state Li-CO2Battery carries out 180 ° of bendings.
Figure 12 is 180 ° of all solid state Li-CO of bending2The chemical property of battery, 2.4V or so is pressed in electric discharge, in charging It is pressed in 3.5V or so.Contrasted with Figure 11, either under 180 ° of bending or formation state, all solid state Li-CO2Secondary cell Prolonged charge and discharge cycles can be realized.
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：By all solid state Li-CO2Battery carries out 360 ° of windings, and it is all solid state that soft-package battery is wrapped in composition wound form on plastic mould Li-CO2Battery.
Figure 13 is wound around 360 ° of all solid state Li-CO2The chemical property of battery.2.4V or so is pressed in electric discharge, in charging It is pressed in 3.5V or so.Contrasted with Figure 11, it is clear that under 360 ° of winding or formation state, all solid state Li-CO2Secondary cell To realize prolonged charge and discharge cycles.
It is an object of the invention to provide a kind of more wall carbon pipes and nickel foam based on the compound high conductivity of solid electrolyte Collector, form the Li-CO for including integrated positive pole2Secondary cell energy storage system, discharge process can be by CO2Efficiently it is reduced into Carbon and lithium carbonate, while discharge electric energy.The all solid state Li-CO2Secondary cell does not have electrolyte volatilization, it is therefore prevented that leakage problem, Improve battery security and stability.There is the secondary cell vast capacity, high temperature can run, be environment-friendly, it is inexpensive and The characteristics of long-life；Its preparation method is simple to operate, controllability is strong, uniformity is good, is advantageous to mass produce, is expected into the future For commercialized new battery system.

Claims (6)

  1. A kind of 1. all solid state Soft Roll formula Li-CO2Secondary cell, it is characterised in that：By lithium piece, composite integrated positive pole and plastic foil The soft-package battery that outer packing assembles, wherein lithium piece are negative pole, and composite integrated positive pole polymerize comprising all solid state inorganic-organic Thing composite membrane electrolyte and the foamed nickel current collector for being loaded with CNT.
  2. 2. all solid state Soft Roll formula Li-CO according to claim 12Secondary cell, it is characterised in that：The composite integrated is just Positive conductive agent in extremely is CNT；Collector is nickel foam；All solid state inorganic-organic polymer composite membrane electrolyte is Poly- (methacrylate) (PMA)/PEG (PEG-600)-LiClO4-SiO2Composite polymer electrolyte (CPE), it is multiple It is 50-150 μm to close film thickness.
  3. 3. all solid state Soft Roll formula Li-CO according to claim 12Secondary cell, it is characterised in that it is described it is all solid state it is inorganic-have The preparation of machine composite membrane of polymer electrolyte solution, comprises the following steps：
    Use quality fraction is used as initiator for the 1-3% of methacrylate (MA) monomer azodiisobutyronitrile (AIBN), Trigger MA polymerizations.Specific method is, by load weighted AIBN initiators, to be added in MA/PEG mixed solutions and gathered at 65 DEG C Reaction 30 minutes is closed, obtains the weight of poly- (methacrylate)/PEG mixture (PMA/PEG), wherein PMA and PEG Amount is than being 65:35；Mass fraction is accounted for PMA/PEG total amounts 0-10% gas phase SiO2Nano particle is added to 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 for 2 hours under mechanical agitation and ul-trasonic irradiation, obtains all solid state inorganic-organic hybrid polymer Electrolyte (CPE) solution.
  4. 4. all solid state Soft Roll formula Li-CO according to claim 12Secondary cell, it is characterised in that the composite integrated positive pole Preparation, comprise the following steps：CNT (CNT) is scattered in 1-METHYLPYRROLIDONE (NMP) solution, and adds quality 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 Nickel foam is rolled into the nickel foam that thickness is 0.8mm；Obtained homogeneous dispersion is coated on the nickel foam afflux after roll-in On body, 120 DEG C of drying in oven are placed in, prefabricated positive pole is made.By all solid state inorganic-organic hybrid polymer dielectric (CPE) solution repeats to cast on prefabricated positive pole, then 60 DEG C of dryings 10 hours in an oven, obtains composite integrated positive pole.
  5. A kind of 5. all solid state Soft Roll formula Li-CO as claimed in claim 12The preparation method of secondary cell, it is characterised in that：By lithium Piece flattens the electrolyte side for being placed in composite integrated positive pole, forms battery core by overlapped way, then inserts plastic-aluminum combined In film shell, and encapsulate sealing.
  6. 6. all solid state Soft Roll formula Li-CO according to claim 52The preparation method of secondary cell, it is characterised in that described soft The size of bag battery is length of side 200mm, thick 2mm.
CN201710858170.7A 2017-09-21 2017-09-21 A kind of all solid state Soft Roll formula lithium carbon dioxide secondary cell and preparation method thereof Pending CN107681161A (en)

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CN109301403A (en) * 2018-10-11 2019-02-01 东北大学 A kind of metal-gas cell system
CN111554916A (en) * 2020-05-18 2020-08-18 南开大学 Quasi-solid state flexible Na-O2Room temperature secondary battery and preparation method thereof
CN112201848A (en) * 2020-09-03 2021-01-08 华中科技大学 Solid electrolyte, composite integrated anode, integrated battery and preparation method thereof
CN112201848B (en) * 2020-09-03 2022-04-12 华中科技大学 Solid electrolyte, composite integrated anode, integrated battery and preparation method thereof

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Application publication date: 20180209