CN108448063A - A kind of guard method of alkali metal secondary battery metal negative electrode - Google Patents
A kind of guard method of alkali metal secondary battery metal negative electrode Download PDFInfo
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- CN108448063A CN108448063A CN201711288423.8A CN201711288423A CN108448063A CN 108448063 A CN108448063 A CN 108448063A CN 201711288423 A CN201711288423 A CN 201711288423A CN 108448063 A CN108448063 A CN 108448063A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- 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
Abstract
The present invention relates to a kind of guard methods of alkali metal secondary battery metal negative electrode；Alkali metal secondary battery includes the battery as cathode with lithium metal, metallic sodium and metallic potassium；Guard method achievees the purpose that protect alkali metal cathode by designing one layer of adding layers in battery alkali metal negative terminal surface.By this simple method, under the premise of not changing alkali metal battery conventional fabrication processes, dendrite of the alkali metal cathode in battery charge and discharge process can be efficiently controlled to be formed, improve the safety of battery, and significantly promote the charge-discharge velocity and cycle life of battery metal cathode, the overpotential of battery cathode is reduced, there is high practical value.
Description
Technical field
The present invention relates to electrochemical technology field and electric energy technical field of energy storage, specially a kind of alkali metal secondary battery gold
Belong to the guard method of cathode.
Background technology
For lithium anode due to its theoretical capacity height, potential is low, has more than the carbon based negative electrodes used in current lithium ion battery
Big advantage.However still having some stubborn problems urgently to be resolved hurrily, lithium anode surface can generate in charge and discharge process
Dendrite, the growth of Li dendrite threaten the safe handling of lithium metal battery.Similarly, sodium metal battery and potassium metal battery is negative
Pole interface is more more unstable than lithium metal, is faced with severeer safety problem.
In the recent period to protecting the research of lithium anode to focus primarily upon optimization, the solid electrolyte membrane of electrolyte（SEI films）
Modification, the improvement of diaphragm and the structure design etc. of collector.Such as：Fluorine-containing additive is added in the electrolytic solution to make
Negative terminal surface is more easy to generate stable solid electrolyte membrane（SEI films）To inhibit the generation of Li dendrite；Or it is artificial in metal
Lithium surface manufactures one layer of artificial solid electrolyte membrane（SEI films）To achieve the purpose that stable metal lithium；Or battery diaphragm is carried out
Some functional processings so that diaphragm machinery strength enhancing, to make the Li dendrite of generation be not easy to pierce through diaphragm generation short circuit；
Also a few thing is converted to three-dimensional afflux by the functionalized design to negative current collector, such as by traditional two-dimentional collector
Body is formed to alleviate the dendrite of cathode.These methods are in protection metal negative electrode, and effect is fine but more in terms of improving stability test
Counting method has the manufacturing cost of higher lithium an- ode, and method is complicated, and operation is difficult to grasp, and is manufactured with existing lithium metal
Technique is incompatible, and for sodium metal battery of the same clan and potassium metal battery, same method is simultaneously not suitable for.
Invention content
In order to solve prior art alkali metal cathode a series of problems present in secondary cell cyclic process, the present invention
A kind of guard method of simple and effective alkali metal cathode is proposed, one layer of adding layers are set in battery alkali metal negative terminal surface,
By disperseing the current density of alkali metal negative terminal surface, the surface area of bigger is provided for the deposition of lithium ion and dissolving so that bear
The alkali metal of pole does not generate the dendrite that can pierce through diaphragm during cycle, while being produced in cyclic process for alkali metal cathode
Raw volume expansion provides certain space, realizes the effect of protection alkali metal cathode.
The invention discloses a kind of guard method of alkali metal secondary battery metal negative electrode, the alkali metal secondary battery gold
The guard method for belonging to cathode is that adding layers are arranged on alkali metal secondary battery metal negative electrode surface to realize alkali metal secondary battery gold
The protection for belonging to cathode reaches and improves metal negative electrode cyclical stability and cycle life, reduces the mistake in metal negative electrode cyclic process
The purpose of potential.
In the present invention, the structure of the adding layers is membrane structure or thin web frame.
In the present invention, the materials of the adding layers include one kind in carbon material, metal, compound, conducting polymer or
Several, the material of adding layers refers to the material for forming adding layers.
In the present invention, the metal includes, aluminium, stainless steel, copper；The carbon material includes carbon fiber, carbon pipe, graphene；
The compound includes one or more of oxide, sulfide, nitride, phosphide, carbide, boride；Preferably,
The carbon material includes carbon paper, carbon cloth, 3D graphenes；The metal includes metal nickel screen, metal aluminium net, stainless (steel) wire, metal
Copper mesh；The oxide is transition metal oxide；The sulfide is transient metal sulfide.
It is further preferred that the material of the adding layers is single carbon material, metal or conducting polymer；Or institute
The material for stating adding layers is the composite material that carbon material is formed with compound, and adding layers of the invention are conductive.
In the present invention, the alkali metal includes lithium, sodium or potassium.
The invention discloses a kind of alkali metal secondary battery, including anode, alkali metal cathode, the alkali metal negative terminal surfaces
Equipped with adding layers；The structure of the adding layers is membrane structure, web frame or 3D structures；The material of the adding layers includes carbon materials
One or more of material, metal, compound, conducting polymer；The metal includes, aluminium, stainless steel, copper；The carbon material
Including carbon fiber, carbon pipe, graphene；The compound includes oxide, sulfide, nitride, phosphide, carbide, boronation
One or more of object；It is preferred that the adding layers are carbon paper, carbon cloth, 3D graphenes, metal nickel screen, metal aluminium net, stainless steel
Net, metal copper mesh, conducting polymer film；Or the adding layers are carbon pipe or graphene and transient metal sulfide, transition gold
Belong to the composite material that oxide is formed；Most preferably carbon paper can obtain most excellent technique effect.
The invention discloses a kind of preparation methods of alkali metal secondary battery, on alkali metal secondary battery metal negative electrode surface
Adding layers are set, and alkali metal secondary battery is formed with alkali metal secondary battery general components；The structure of the adding layers is film
Structure, web frame or 3D structures；The material of the adding layers includes one in carbon material, metal, compound, conducting polymer
Kind is several；The metal includes, aluminium, stainless steel, copper；The carbon material includes carbon fiber, carbon pipe, graphene；The chemical combination
Object includes one or more of oxide, sulfide, nitride, phosphide, carbide, boride；It is preferred that the adding layers
For carbon paper, carbon cloth, 3D graphenes, metal nickel screen, metal aluminium net, stainless (steel) wire, metal copper mesh, conducting polymer film；Or institute
It is the composite material that carbon pipe or graphene are formed with transient metal sulfide, transition metal oxide to state adding layers；Most preferably carbon
Paper can obtain most excellent technique effect.
The invention also discloses adding layers protection alkali metal secondary battery metal negative electrode or preparing alkali metal it is secondary
Application in battery；The structure of the adding layers is membrane structure or thin web frame；The material of the adding layers includes carbon materials
One or more of material, metal, compound, conducting polymer；The metal includes, aluminium, stainless steel, copper；The carbon material
Including carbon fiber, carbon pipe, graphene；The compound includes oxide, sulfide, nitride, phosphide, carbide, boronation
One or more of object；It is preferred that the adding layers are carbon paper, carbon cloth, 3D graphenes, metal nickel screen, metal aluminium net, stainless steel
Net, metal copper mesh, conducting polymer film；Or the adding layers are carbon pipe or graphene and transient metal sulfide, transition gold
Belong to the composite material that oxide is formed；Most preferably carbon paper can obtain most excellent technique effect.
The present invention by the battery structure of traditional positive electrode/diaphragm/alkali metal cathode be improved to positive electrode/diaphragm/
The battery structure of adding layers/alkali metal cathode, the adding method of the adding layers of alkali metal secondary battery are directly to press from both sides adding layers
Between cathode alkali metal and battery diaphragm or for the battery without diaphragm, adding layers directly overlay negative when battery assembles
Pole alkali metal surface.
The applicable secondary cell system of the method for the present invention is very extensive, other general components of battery in addition to adding layers can
Arbitrary collocation；Alkali metal secondary battery general components may include：With alkali metal cathode pairing cell positive material, battery every
Film type, electrolyte, electrolyte system, battery types.Such as：
Cell positive material includes anode material of lithium battery：Lithium iron phosphate positive material；Lithium cobalt oxide, lithium manganese oxygen, lithium nickel oxygen binary
Composite positive pole；Li-Ni-Mn-O ternary composite cathode material；The sulphur composite positive pole of lithium-sulfur cell；Lithium-oxygen battery and lithium are empty
The oxygen and catalyst composite in pneumoelectric pond etc. and sode cell positive electrode and potassium cell positive material.
Battery diaphragm, including PP films；PE films；PP/PE films；PP/PE/PP films；Glass fibre element diaphragm；Non-woven membrane etc..
Electrolyte, including double trifluoromethanesulfonimides lithium/sodium/potassium（Li/Na/KTFSI）；Trifluoromethanesulfonimide
Lithium/sodium/potassium（Li/Na/KFSI）；Lithium hexafluoro phosphate（Li/Na/KPF6）；Lithium perchlorate/sodium/potassium（Li/Na/KClO4）；Tetrafluoro
Lithium borate/sodium/potassium（Li/Na/KBF4）；Di-oxalate lithium borate/sodium/potassium（Li/Na/KBOB）Deng.
Electrolyte system, including carbonates organic electrolyte system；Ethers organic electrolyte system；Aqueous electrolyte；
Solid state electrolysis plastidome etc..
Electrolytic cell type, including button cell, soft-package battery, column battery etc..
Due to the application of the above technical scheme, the present invention has the following advantages that compared with prior art：
1, it is provided by the present invention protection alkali metal cathode method protecting effect it is notable, extend metal negative electrode cycle life and
Reducing metal negative electrode overpotential has unrivaled advantage.
Even if 2, the method for protection alkali metal cathode provided by the present invention is under conditions of great current density, cathode
Metal remains to stability and high efficiency cycle thousands of times.
3, the method that can only realize lithium anode protection compared to current major part, protection alkali gold provided by the present invention
The guard method for belonging to cathode, can be applied not only to lithium anode, and can continue to use negative to metallic sodium cathode of the same clan and metallic potassium
Pole has wide range of applications.
4, the method for protection alkali metal cathode provided by the present invention is applicable to different battery systems, battery size,
It has wide range of applications.
5, the method for protection alkali metal cathode provided by the present invention, method is simple, can not change existing alkali metal
Significant protecting effect is realized under conditions of manufacturing process.
Description of the drawings
Fig. 1 is the cycle number of turns-voltage curve of the lithium metal Symmetrical cells of the carbon paper protection in embodiment one；
Fig. 2 is the cycle number of turns-voltage curve of the lithium metal Symmetrical cells of the carbon paper protection in embodiment two；
Fig. 3 is the cycle number of turns-voltage curve of the lithium metal Symmetrical cells of the carbon paper protection in embodiment three；
Fig. 4 is the cycle number of turns-voltage curve of the lithium metal Symmetrical cells of the metal aluminium net in example IV；
Fig. 5 is the cycle number of turns-voltage curve of the metallic sodium Symmetrical cells of the carbon paper protection in embodiment five；
Fig. 6 is the cycle number of turns-voltage curve of the metallic sodium Symmetrical cells of the carbon paper protection in embodiment six；
Fig. 7 is the cycle number of turns-voltage curve of the metallic potassium Symmetrical cells of the carbon paper protection in embodiment seven；
Fig. 8 is the cycle number of turns-voltage curve of the lithium metal Symmetrical cells of the carbon paper protection in comparative example one；
Fig. 9 is the cycle number of turns-voltage curve of the metallic sodium Symmetrical cells of the carbon paper protection in comparative example two；
Figure 10 is the cycle number of turns-voltage curve of the metallic potassium Symmetrical cells of the carbon paper protection in comparative example three.
Specific implementation mode
The invention will be further described with reference to the accompanying drawings and embodiments.It should be noted that the case where not conflicting
Under, the features in the embodiments and the embodiments of the present application mutually can be combined arbitrarily.
The lithium metal Symmetrical cells that carbon paper is protected under one ethers electrolyte system small current density of embodiment
Symmetrical cells assemble：Battery size is CR2032, and diaphragm uses PP, and it is double three that electrolyte, which selects ethers electrolyte, solute,
Fluoromethane sulfimide lithium（LiTFSI）；Solvent is 1,3- dioxolanes and glycol dimethyl ether（DOL/DME）By volume
1:1 mixed liquor；Solute concentration is 1 M.Battery structure is lithium metal/carbon paper/diaphragm/carbon paper/lithium metal.
It in current density is 0.5 mA/cm that attached drawing 1, which is the battery,2Under cyclic curve.The deposition of lithium metal in the battery/
Dissoluble capacity is 1 mAh/cm2.In conjunction with Fig. 1, the lithium metal deposition of the lithium metal Symmetrical cells prepared by this method/dissolved electricity
Gesture is 20 mV, and lithium anode can stablize the circle of continuous deposition/dissolving circulation 800, thus prove to be used as adding layers energy by carbon paper
It restrained effectively Li dendrite free growth and pierce through battery short circuit problem caused by diaphragm, be effectively protected in cyclic process
Lithium anode.
The lithium metal Symmetrical cells that carbon paper is protected under high current density in two ethers electrolyte system of embodiment
Symmetrical cells assemble：Battery size is CR2032, and diaphragm uses PP, and it is double three that electrolyte, which selects ethers electrolyte, solute,
Fluoromethane sulfimide lithium（LiTFSI）；Solvent is 1,3- dioxolanes and glycol dimethyl ether（DOL/DME）By volume
1:1 mixed liquor；Solute concentration is 1 M.Battery structure is lithium metal/carbon paper/diaphragm/carbon paper/lithium metal.
It in current density is 5 mA/cm that attached drawing 2, which is the battery,2Under cyclic curve.The deposition of lithium metal in the battery/molten
Solution capacity is 1 mAh/cm2.In conjunction with Fig. 2, the lithium metals of the lithium metal Symmetrical cells prepared by this method deposits/dissolve overpotential
For 200 mV or so, lithium anode can stablize the circle of continuous deposition/dissolving circulation 4000, and in conjunction with the embodiments one, it was demonstrated that pass through carbon
Paper can not only restrained effectively Li dendrite free growth as adding layers under the conditions of low current and pierce through battery caused by diaphragm
Short circuit problem realizes the protection of cathode, equally has remarkable lithium anode protective capability under conditions of high current density.
The lithium metal Symmetrical cells that carbon paper is protected in embodiment thricarbonate esters electrolyte system
Symmetrical cells assemble：Battery size is CR2032, and diaphragm uses PP, electrolyte to select esters electrolyte, and solute is hexafluoro
Lithium phosphate（LiPF6）；Solvent is ethylene carbonate and diethyl carbonate（EC/DEC）By volume 1:1 mixed liquor；Solute is dense
Degree is 1 M.Battery structure is lithium metal/carbon paper/diaphragm/carbon paper/lithium metal.
It in current density is 0.5 mA/cm that attached drawing 3, which is the battery,2Under cyclic curve.The deposition of lithium metal in the battery/
Dissoluble capacity is 1 mAh/cm2.In conjunction with Fig. 3, the lithium metal deposition of the lithium metal Symmetrical cells prepared by this method/dissolved electricity
Gesture is 15 mV, and lithium anode can stablize the circle of continuous deposition/dissolving circulation 120, in conjunction with the embodiments one, it was demonstrated that made by carbon paper
Li dendrite free growth can not only be restrained effectively in ethers electrolyte system for adding layers pierces through battery caused by diaphragm
Short circuit problem realizes the protection of cathode, and the protection of lithium metal can be equally realized in carbonates electrolyte.
The lithium metal Symmetrical cells of example IV metal aluminium net protection
Symmetrical cells assemble：Battery size is CR2032, and diaphragm uses PP, electrolyte to select esters electrolyte, and solute is hexafluoro
Lithium phosphate（LiPF6）；Solvent is ethylene carbonate and diethyl carbonate（EC/DEC）By volume 1:1 mixed liquor；Solute is dense
Degree is 1 M.Battery structure is lithium metal/metal aluminium net/diaphragm/metal aluminium net/lithium metal.
It in current density is 1 mA/cm that attached drawing 4, which is the battery,2Under cyclic curve.The deposition of lithium metal in the battery/molten
Solution capacity is 1 mAh/cm2.In conjunction with Fig. 4, the lithium metals of the lithium metal Symmetrical cells prepared by this method deposits/dissolve overpotential
Between 100-600 mV, increases overpotential with the cycle number of turns and slowly increase, lithium anode can stablize continuous deposition/dissolving and follow
Ring 200 encloses, and in conjunction with the embodiments one, it was demonstrated that replace metal aluminium net and can equally restrained effectively Li dendrite as adding layers and freely give birth to
It is long to pierce through battery short circuit problem caused by diaphragm, realize the protection of cathode.
The metallic sodium Symmetrical cells that carbon paper is protected under five ethers electrolyte system small current density of embodiment
Symmetrical cells assemble：Battery size is CR2032, and diaphragm uses PP, electrolyte to select ethers electrolyte, and solute is trifluoro
Methanesulfonic sodium（NaSO3CF3）；Solvent is diethylene glycol dimethyl ether（DGME）；Solute concentration is 1 M.Battery structure be metallic sodium/
Carbon paper/diaphragm/carbon paper/metallic sodium.
It in current density is 0.5 mA/cm that attached drawing 5, which is the battery,2Under cyclic curve.The deposition of metallic sodium in the battery/
Dissoluble capacity is 1 mAh/cm2.In conjunction with Fig. 5, the metal sodian deposition of the metallic sodium Symmetrical cells prepared by this method/dissolved electricity
Gesture is 20 mV, and metallic sodium cathode can stablize the circle of continuous deposition/dissolving circulation 260, thus proves that being used as adding layers by carbon paper exists
Metallic sodium cathode is effectively protected in cyclic process.
The metallic sodium Symmetrical cells that carbon paper is protected under high current density in six ethers electrolyte system of embodiment
Symmetrical cells assemble：Battery size is CR2032, and diaphragm uses PP, electrolyte to select ethers electrolyte, and solute is trifluoro
Methanesulfonic sodium（NaSO3CF3）；Solvent is diethylene glycol dimethyl ether（DGME）；Solute concentration is 1 M.Battery structure be metallic sodium/
Carbon paper/diaphragm/carbon paper/metallic sodium.
It in current density is 5 mA/cm that attached drawing 6, which is the battery,2Under cyclic curve.The deposition of metallic sodium in the battery/molten
Solution capacity is 1 mAh/cm2.In conjunction with Fig. 6, by metal sodian deposition/dissolving overpotential of metallic sodium Symmetrical cells prepared by this method
For 50-100 mV, metallic sodium cathode can stablize the circle of continuous deposition/dissolving circulation 1200, and in conjunction with the embodiments five, it was demonstrated that pass through carbon paper
The protection that metallic sodium cathode can not only be effectively realized under the conditions of low current as adding layers, under conditions of high current density
It is same that there is remarkable metallic sodium cathode protective capability.
The metallic potassium Symmetrical cells of seven carbon paper of embodiment protection
Symmetrical cells assemble：Battery size is CR2032, and diaphragm uses PP, electrolyte to select ethers electrolyte, and solute is hexafluoro
Potassium phosphate（KPF6）；Solvent is ethylene carbonate and diethyl carbonate（EC/DEC）By volume 1:1 mixed liquor；Solute concentration
For 1 M.Battery structure is metallic potassium/carbon paper/diaphragm/carbon paper/metallic potassium.
It in current density is 0.5 mA/cm that attached drawing 7, which is the battery,2Under cyclic curve.The deposition of lithium metal in the battery/
Dissoluble capacity is 1 mAh/cm2.In conjunction with Fig. 7, the lithium metal deposition of the metallic potassium Symmetrical cells prepared by this method/dissolved electricity
Gesture is 20 mV or so, and metallic potassium cathode can stablize the circle of continuous deposition/dissolving circulation 300, thus prove to be used as addition by carbon paper
Layer equally can be effectively protected metallic potassium cathode.
Comparative example one does not do the lithium metal Symmetrical cells of any protection
Symmetrical cells assemble：Battery size is CR2032, and diaphragm uses PP, and it is double three that electrolyte, which selects ethers electrolyte, solute,
Fluoromethane sulfimide lithium（LiTFSI）；Solvent is 1,3- dioxolanes and glycol dimethyl ether（DOL/DME）By volume
1:1 mixed liquor；Solute concentration is 1 M.Battery structure is lithium metal/diaphragm/lithium metal.
It in current density is 0.5 mA/cm that attached drawing 8, which is the battery,2Under cyclic curve.The deposition of lithium metal in the battery/
Dissoluble capacity is 1 mAh/cm2.In conjunction with Fig. 8, the lithium metal deposition of the lithium metal Symmetrical cells of any protection/dissolved electricity is not done
Originally gesture is 15 mV or so, subsequent overpotential is increased rapidly with cycle, lithium anode only deposition/dissolving circulation 100
Circle, cathode are unstable.
Comparative example two does not do the metallic sodium Symmetrical cells of any protection
Symmetrical cells assemble：Battery size is CR2032, and diaphragm uses PP, electrolyte to select ethers electrolyte, and solute is trifluoro
Methanesulfonic sodium（NaSO3CF3）；Solvent is diethylene glycol dimethyl ether（DGME）；Solute concentration is 1 M.Battery structure be metallic sodium/
Diaphragm/metallic sodium.
It in current density is 0.5 mA/cm that attached drawing 9, which is the battery,2Under cyclic curve.The deposition of lithium metal in the battery/
Dissoluble capacity is 1 mAh/cm2.In conjunction with Fig. 9, not doing the metallic sodium of the metallic sodium Symmetrical cells of any protection can hardly complete
Deposition/dissolving circulation, overpotential is very big, and cathode is extremely unstable.
Comparative example three does not do the metallic potassium Symmetrical cells of any protection
Symmetrical cells assemble：Battery size is CR2032, and diaphragm uses PP, electrolyte to select ethers electrolyte, and solute is hexafluoro
Potassium phosphate（KPF6）；Solvent is ethylene carbonate and diethyl carbonate（EC/DEC）By volume 1:1 mixed liquor；Solute concentration
For 1 M.Battery structure is metallic sodium/diaphragm/metallic sodium.
It in current density is 0.5 mA/cm that attached drawing 10, which is the battery,2Under cyclic curve.Lithium metal is heavy in the battery
Product/dissoluble capacity is 1 mAh/cm2.In conjunction with Figure 10, the metallic potassium for not doing the metallic potassium Symmetrical cells of any protection is only capable of completing
20 circle deposition/dissolving circulations, and overpotential is very big, cathode is extremely unstable.
Therefore, the present invention provides a kind of guard methods of simple and effective lithium an- ode, and same method can
To be transplanted in the cathode protection of sodium metal battery and potassium metal battery.Even if not changing the conventional fabrication processes of alkali metal
In the case of remain to significantly improve alkali metal cathode cycle life, reduce battery cathode overpotential.With high practical valence
Value.
Claims (10)
1. a kind of guard method of alkali metal secondary battery metal negative electrode, it is characterised in that：The alkali metal secondary battery metal
The guard method of cathode is that adding layers are arranged on alkali metal secondary battery metal negative electrode surface to realize alkali metal secondary battery metal
The protection of cathode.
2. the guard method of alkali metal secondary battery metal negative electrode according to claim 1, which is characterized in that the adding layers
Structure be membrane structure or thin web frame.
3. the guard method of alkali metal secondary battery metal negative electrode according to claim 1, which is characterized in that the adding layers
Material include one or more of carbon material, metal, compound, conducting polymer.
4. the guard method of alkali metal secondary battery metal negative electrode according to claim 3, which is characterized in that the metal packet
Include aluminium, iron, cobalt, nickel, copper, zinc, stainless steel；The carbon material includes carbon fiber, carbon pipe, graphene；The compound includes oxygen
One or more of compound, sulfide, nitride, phosphide, carbide, boride.
5. the guard method of alkali metal secondary battery metal negative electrode according to claim 4, which is characterized in that the carbon material
Including carbon paper, carbon cloth, 3D graphenes；The metal includes metal nickel screen, metal aluminium net, stainless (steel) wire, metal copper mesh, foam
Nickel, foam copper.
6. the guard method of alkali metal secondary battery metal negative electrode according to claim 3, which is characterized in that the adding layers
Material be single carbon material, metal or conducting polymer；Or the material of the adding layers is carbon material and compound
The composite material of formation.
7. the guard method of alkali metal secondary battery metal negative electrode according to claim 1, which is characterized in that the alkali metal
Including lithium, sodium or potassium.
8. a kind of alkali metal secondary battery, including anode, metal negative electrode；Add it is characterized in that, the metal negative electrode surface is equipped with
Add layer；The structure of the adding layers is membrane structure or thin web frame；The material of the adding layers include carbon material, metal,
One or more of compound, conducting polymer；The metal includes, aluminium, stainless steel, copper；The carbon material includes carbon fiber
Dimension, carbon pipe, graphene；The compound includes one in oxide, sulfide, nitride, phosphide, carbide, boride
Kind is several.
9. alkali metal secondary battery according to claim 8, which is characterized in that the adding layers are carbon paper, carbon cloth, 3D graphite
Alkene, metal nickel screen, metal aluminium net, stainless (steel) wire, metal copper mesh, conducting polymer film；Or the adding layers are carbon pipe or stone
The composite material that black alkene is formed with transient metal sulfide, transition metal oxide.
10. adding layers are protecting alkali metal secondary battery metal negative electrode or the application in preparing alkali metal secondary battery,
It is characterized in that, the structure of the adding layers is membrane structure or thin web frame；The material of the adding layers includes carbon material, gold
One or more of category, compound, conducting polymer；The metal includes, aluminium, stainless steel, copper；The carbon material includes carbon
Fiber, carbon pipe, graphene；The compound includes in oxide, sulfide, nitride, phosphide, carbide, boride
It is one or more of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711288423.8A CN108448063A (en) | 2017-12-07 | 2017-12-07 | A kind of guard method of alkali metal secondary battery metal negative electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711288423.8A CN108448063A (en) | 2017-12-07 | 2017-12-07 | A kind of guard method of alkali metal secondary battery metal negative electrode |
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| CN109244441A (en) * | 2018-08-29 | 2019-01-18 | 浙江大学 | Non-newtonian flow posture Na-K alloy electrode and its preparation method and application |
| CN111180672A (en) * | 2020-01-19 | 2020-05-19 | 中南大学 | Protection method of alkali metal cathode, cathode prepared by protection method and application of cathode |
| WO2020192167A1 (en) * | 2019-03-25 | 2020-10-01 | Ningde Amperex Technology Limited | Anode, and electrochemical device and electronic device comprising same |
| CN112436107A (en) * | 2019-08-26 | 2021-03-02 | 青岛九环新越新能源科技股份有限公司 | Battery based on metal electrode |
| CN112436106A (en) * | 2019-08-26 | 2021-03-02 | 青岛九环新越新能源科技股份有限公司 | Metal positive electrode and battery based on metal positive electrode |
| CN112436140A (en) * | 2019-08-26 | 2021-03-02 | 青岛九环新越新能源科技股份有限公司 | Composite material for inhibiting dendritic crystal growth |
| TWI803088B (en) * | 2020-12-28 | 2023-05-21 | 財團法人工業技術研究院 | Negative electrode and lithium ion battery employing the same |
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| TWI803088B (en) * | 2020-12-28 | 2023-05-21 | 財團法人工業技術研究院 | Negative electrode and lithium ion battery employing the same |
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