CN109037626A - A kind of alkali metal base cathode and its preparation method and application - Google Patents

A kind of alkali metal base cathode and its preparation method and application Download PDF

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CN109037626A
CN109037626A CN201810805324.0A CN201810805324A CN109037626A CN 109037626 A CN109037626 A CN 109037626A CN 201810805324 A CN201810805324 A CN 201810805324A CN 109037626 A CN109037626 A CN 109037626A
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alkali metal
fluorinated
carbon
base cathode
metal base
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CN109037626B (en
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谢健
成浩
毛阳俊
曹高劭
赵新兵
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Zhejiang University ZJU
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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
    • 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
    • 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
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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

Abstract

The invention discloses a kind of alkali metal base cathode and its preparation method and application, which includes alkali metal, and the fluorinated carbon material being uniformly distributed in alkali metal.Fluorinated carbon material is introduced into alkali metal by the present invention, the fluoride of alkali metal can be formed in situ in charge and discharge process, the fluoride and carbon material form synergistic effect, uniform electric field is formed in charge and discharge process, to promote the uniform deposition of alkali metal, effectively inhibit the formation of alkali metal dendrite and the interfacial reaction of alkali metal and electrolyte, improves the security performance and cyclical stability of alkali metal battery.

Description

A kind of alkali metal base cathode and its preparation method and application
Technical field
The present invention relates to the technical fields of energy-storage battery, and in particular to a kind of alkali metal base cathode and preparation method thereof and answers With.
Background technique
Although lithium ion battery still occupies leading position in the secondary battery, as new-energy automobile is to lithium-ion electric Energy density requirement in pond is higher and higher, and the energy density of traditional lithium ion battery based on insertion reaction has reached the limit, i.e., Bottleneck value is had been approached by the energy density of the lithium ion battery of cathode of graphite, exploitation is using lithium metal as the lithium battery (packet of cathode Include lithium-sulfur cell, lithium sky battery) it is imperative.On the other hand, with the development of new-energy automobile, the consumption of lithium resource quickly, But the reserves of lithium on earth are very limited, and in contrast, the reserves of sodium and potassium are relatively abundant, can satisfy large-scale use. Therefore, it develops the novel battery based on sodium and potassium and has become the hot spot currently researched and developed.
It but a use of fatal problem of the battery that alkali metal is cathode is directly alkali metal meeting in charge and discharge cycles Li dendrite is formed, the safety problem of battery is caused.In addition, the compatibility of alkali metal and liquid electrolyte and some solid electrolytes Poor, long-term circulation will lead to the corrosion of alkali metal or the formation of interface passivation layer, to reduce the cycle life of battery.Cause This, in order to improve safety and the service life of alkali metal battery, it is necessary to make protection processing to alkali metal.
Previous research concentrates on carbon material and fluoride protects alkali metal, such as Publication No. CN 108063218 A kind of preparation method of sheet metal lithium base cathode is disclosed in the Chinese patent literature of A, first copper foil current collector has been base to cathode Bottom synthesizes single-layer graphene film on copper foil current collector surface using chemical vapour deposition technique, the graphene supported with this copper foil For cathode, anode is made with rich lithium material or lithium salts and forms into lithium battery, then applying electric current keeps the lithium in rich lithium material or lithium salts heavy Product obtains lithium metal/graphene composite negative, although can be obtained with this method relatively uniform in the graphene that copper foil supports Composite negative pole is suitable for than relatively thin electrode, but when electrode is thicker, easily causes lithium to be distributed in graphene uneven, separately Outside, although carbon material to inhibit Li dendrite effect it is preferable, electrode is protected, inhibit with the reaction effect of electrolyte compared with It is weak.
It for another example authorizes in the Chinese patent literature of Publication No. CN 207441857U and discloses a kind of lithium metal/artificial nothing Machine salt combination electrode, the combination electrode are obtained after metallic lithium surface deposited inorganic using magnetron sputtering method, the inorganic matter Such as lithium fluoride, lithium bromide, lithium chloride, this method although available relatively uniform surface coating layer, but be equally suitable only for In thin electrode, and it is not easy to realize large scale preparation, in addition, since inorganic matter conductivity is lower, simple inorganic compound Introduce the decline that will cause electrode conductivity.
Summary of the invention
The invention discloses a kind of novel alkali metal base cathode, and formation and the alkali metal of alkali metal dendrite can be effectively suppressed With the interfacial reaction of electrolyte, the security performance and cyclical stability of alkali metal battery are improved.
Specific technical solution is as follows:
A kind of alkali metal base cathode, including alkali metal, and the fluorinated carbon material being uniformly distributed in alkali metal.
Fluorinated carbon material is introduced into alkali metal for the first time by the present invention, and alkali metal can be formed in situ in charge and discharge process Fluoride, since the fluoride and carbon material of alkali metal are in close contact, there are bonding or part bonding action, fluoride and carbon materials Material forms synergistic effect, and uniform electric field is formed in charge and discharge process, to promote the uniform deposition of alkali metal, effectively inhibits The formation of alkali metal dendrite improves the safety of alkali metal battery；On the other hand, the fluoride and carbon material being formed in situ will have Effect protection alkali metal inhibits reacting for alkali metal and organic bath or solid electrolyte, the boundary of raising alkali metal and electrolyte Face stability is to improve the cycle life of battery；Furthermore the conductivity of composite negative pole can be improved in the carbon material introduced in situ, To reduce polarization of electrode.
So-called polarization, the absolute value of deviation from origin when referring to electrode charge or electric discharge.
It is found through experiment that when using the technical solution for being directly added into fluoride and carbon material, since fluoride is in carbon materials It is difficult to realize bonding action that is evenly dispersed, being more difficult realization the two in material, cannot achieve the synergistic effect of the two to inhibit alkali golden The formation and protection alkali metal, the Local enrichment of the fluoride of low conductivity for belonging to dendrite also will lead to the increase of electrode polarization, from And cause the high polarization of electrode and short cycle life.
The alkali metal is selected from least one of lithium, sodium, potassium；
The fluorinated carbon material is soft selected from fluorinated nano carbon pipe, fluorinated carbon fiber, fluorinated graphene, fluorination hard carbon, fluorination At least one of carbon, fluorinated fullerene, fluorographite.
Preferably, the weight ratio of the alkali metal base cathode, fluorinated carbon material and alkali metal is 1~20:100.The alkali In Metal Substrate cathode, reasonable alkali metal and fluorination carbon content are conducive in the case where adequately protecting to alkali metal without shadow Ring the capacity and reversible degree of alkali metal cathode.Further preferably, the weight ratio of the fluorinated carbon material and alkali metal be 2.5~ 10:100.In the alkali metal base cathode, too low fluorine content is unfavorable for that alkali metal is effectively protected, due to fluorocarbons Conductivity it is lower, excessively high fluorine content will reduce the conductivity of composite negative pole, to reduce the high rate performance and capacity of cathode. Preferably, in the fluorinated carbon material, fluorine content is 5~65%.Based on the commercialization situation of current fluorinated carbon material, directly select The fluorinated carbon material that commercially available fluorine content is 50% is selected, at this point, can also account for the ratio of raw material gross weight by adjusting fluorinated carbon material Example is adjusted fluorine content.
Preferably, the fluorinated carbon material is powdered, having a size of 10nm~50 μm.Further preferably nanoscale material Material, having a size of 10nm~500nm, so-called nano-scale, as long as the size for meeting at least one direction on three-dimensional is nanometer Grade；Particle size is too small easy to reunite, particle size is excessive be unfavorable for it is evenly dispersed in alkali metal, and in conjunction with alkali metal Power dies down.
Preferably, the fluorinated carbon material is selected from fluorinated nano carbon pipe, fluorinated carbon fiber or fluorinated graphene.
It is further preferred:
The fluorinated carbon material is selected from fluorinated nano carbon pipe；
The weight ratio of the fluorinated carbon material and alkali metal is 2.5~5:100；The diameter of the fluorinated nano carbon pipe is 30 ~60nm, length are 500nm~2 μm, and by weight, fluorine content is 50% in fluorinated nano carbon pipe.
It is found through experiment that with using the battery of the alkali metal base cathode assembling of the above-mentioned raw material preparation advanced optimized, pole Minimum change value is only 22 millivolts.
The invention also discloses the preparation methods of the alkali metal base cathode, using industrialized fluorinated carbon material as raw material, It is prepared using the simple machinery method of mixing, the specific steps are as follows:
1) under inert atmosphere protection, alkali metal is kneaded into flake；
2) carbon fluoride powder uniform load is applied pressure and is allowed to be adhered to alkali metal in alkali metal surface, then through repeatedly Alkali metal base cathode is obtained after folding and rubbing pressure.
In step 1), the inert atmosphere is argon gas, nitrogen or helium, and preferably argon gas is prepared atmosphere.
In step 2), the application pressure is not provided particularly, so that carbon fluoride powder is adhered to alkali metal and does not take off Falling is advisable.
In step 3), folding and number that is rubbing pressure does not have special provision, is dispersed in alkali metal with carbon fluoride powder Uniformly be advisable, it is so-called uniformly, not stringent judgment criteria, visually color of being subject to is uniform and microcosmic powers on sem observation.
The invention also discloses the alkali metal base cathode in alkali metal battery, alkali metal-sulphur battery, alkali metal-sky Application in pneumoelectric pond.
Compared with prior art, the present invention has the advantage that
1, alkali metal base cathode of the invention is mixed using alkali metal and fluorinated carbon material as raw material by simple machinery Fluorinated carbon material is introduced into alkali metal by method, and the fluoride of alkali metal can be formed in situ in charge and discharge process, the fluorine Compound and carbon material form synergistic effect, and uniform electric field is formed in charge and discharge process, to promote the uniform heavy of alkali metal Product effectively inhibits the formation of alkali metal dendrite and the interfacial reaction of alkali metal and electrolyte, improves the safety of alkali metal battery Energy and cyclical stability, meanwhile, conductivity can be improved in the carbon material being formed in situ, and reduces polarization of electrode.
2, the preparation process of alkali metal base cathode uses cheap raw material in the present invention, and simple process, consume energy low, cost Small, the period is short, is conducive to large-scale production.
Detailed description of the invention
Fig. 1 is lithium/fluorinated nano carbon pipe composite negative pole X-ray diffraction (XRD) map prepared by embodiment 1；
Fig. 2 is lithium/fluorinated nano carbon pipe composite negative pole scanning electron microscope (SEM) photo prepared by embodiment 1；
Fig. 3 is that the charge and discharge of the lithium/fluorinated nano carbon pipe composite negative pole assembling Symmetrical cells prepared with embodiment 1 are bent Line；
Fig. 4 is the F1s x-ray photoelectron energy after lithium/fluorinated nano carbon pipe composite negative pole charge and discharge prepared by embodiment 1 It composes (XPS)；
Fig. 5 is the charging and discharging curve of the Symmetrical cells of the cathode of lithium assembling prepared with comparative example 1.
Specific embodiment
Present invention is further described in detail with reference to the accompanying drawings and embodiments, it should be pointed out that following embodiment It is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1
Under argon atmosphere protection, lithium metal is kneaded into flake；By fluorinated nano carbon pipe powder uniform load in metal Lithium surface, applying pressure makes fluorinated nano carbon pipe powder be adhered to metallic lithium surface, the weight and lithium metal of fluorinated nano carbon pipe Weight ratio be 2.5%, the fluorinated volume of fluorinated nano carbon pipe is 50wt%, and the diameter of fluorinated nano carbon pipe is 30~60nm, long Degree is 500nm~2 μm；The alkali metal that area load has fluorinated nano carbon pipe powder is folded and is rubbed pressure, folding again and rub Pressure obtains lithium metal/fluorinated nano carbon pipe composite negative pole.
Fig. 1 is the XRD spectrum of composite negative pole manufactured in the present embodiment, from map it is found that diffraction maximum is lithium peak, fluorinated nano There is not diffraction maximum since content is low, crystallinity is low in figure in carbon pipe.
Fig. 2 is the SEM photograph of composite negative pole manufactured in the present embodiment, from photo it is found that fluorinated nano carbon pipe is in lithium metal Middle dispersion is relatively uniform.
Fig. 3 is the charging and discharging curve of the Symmetrical cells assembled with composite negative pole manufactured in the present embodiment (with LiClO4Three Glycol dimethyl ether (TEGDME) solution is electrolyte, and Celgard C480 film is diaphragm).As current density 0.5mA/cm2, hold Amount is 1mAh/cm2When, from figure it is found that the polarization of Symmetrical cells is only 22 millivolts, as current density 5mA/ by 200 hours cm2, capacity 1mAh/cm2, by 200 hours, the polarization of Symmetrical cells is 99 millivolts, by 400 hours, Symmetrical cells Polarization be 188 millivolts.
Fig. 4 is F1s XPS map of the composite negative pole manufactured in the present embodiment after charge and discharge, from map it is found that foring LiF。
Comparative example 1
The preparation of electrode and the assembly such as embodiment 1 of battery, except that fluorinated nano is not added in lithium metal Carbon pipe, electro-chemical test show (current density 0.5mA/cm under identical testing conditions2, capacity 1mAh/cm2When, pass through 200 hours), polarizing is 34 millivolts, sees Fig. 5.
Comparative example 2
The preparation of electrode and the assembly such as embodiment 1 of battery, except that the general of identical weight is added in lithium metal Logical carbon nanotubes, rather than fluorinated nano carbon pipe, electro-chemical test show (current density 0.5mA/ under identical testing conditions cm2, capacity 1mAh/cm2When, by 200 hours), polarizing is 28 millivolts.
Comparative example 3
The preparation of electrode and the assembly such as embodiment 1 of battery, except that lithium fluoride and nanometer are added in lithium metal The mole of carbon and fluorine is identical in fluorinated nano carbon pipe in the mole with embodiment of fluorine in carbon pipe, carbon nanotubes and lithium fluoride. Electro-chemical test shows (current density 0.5mA/cm under identical testing conditions2, capacity 1mAh/cm2When, by 200 Hour), polarizing is 32 millivolts.
Embodiment 2
The preparation of the electrode of electrode and the assembly such as embodiment 1 of battery, except that fluorinated nano carbon pipe is changed into The identical fluorographite of additive amount, fluorinated volume, electro-chemical test show (current density 0.5mA/ under identical testing conditions cm2, capacity 1mAh/cm2When, by 200 hours), polarizing is 30 millivolts.
Embodiment 3
Under argon atmosphere protection, metallic sodium is kneaded into flake；By fluorinated graphene powder uniform load in metallic sodium Surface, applying pressure makes fluorinated graphene powder be adhered to metallic sodium surface, the weight of fluorinated graphene and the weight of metallic sodium Than being 5%, the fluorinated volume of fluorinated graphene is 50wt%；There is the metallic sodium of fluorinated graphene powder to fold and rub area load It is pressure, folding again and rub pressure and obtain metallic sodium/fluorinated graphene composite negative pole.Product is metallic sodium through XRD characterization, is fluorinated stone There is not diffraction maximum since content is low, crystallinity is low in figure in black alkene.Product is characterized through SEM, and fluorinated graphene is in metallic sodium Middle dispersion is relatively uniform.Electro-chemical test shows (current density 0.5mA/cm2, capacity 1mAh/cm2When, it is small by 200 When), it is only 25mV by the polarization of the Symmetrical cells of electrode of metallic sodium/fluorinated graphene.
Embodiment 4
Under argon atmosphere protection, metallic potassium is kneaded into flake；By fluorinated carbon fiber powder uniform load in metallic potassium Surface, applying pressure makes fluorination Carbon fibe powder be adhered to metallic potassium surface, the weight ratio of fluorinated carbon fiber weight and metallic potassium It is 10%, the fluorinated volume of fluorinated carbon fiber is 50wt%；There is the metallic potassium of fluorinated carbon fiber powder to fold and rub area load It is pressure, folding again and rub pressure and obtain metallic potassium/fluorinated carbon fiber composite negative pole.Product is metallic potassium, fluorocarbons through XRD characterization There is not diffraction maximum since content is low, crystallinity is low in figure in fiber.Product is characterized through SEM, and fluorinated carbon fiber is in metallic potassium Middle dispersion is relatively uniform.Electro-chemical test shows (current density 0.5mA/cm2, capacity 1mAh/cm2When, it is small by 200 When, it is only 32mV by the polarization of the Symmetrical cells of electrode of metallic potassium/fluorinated carbon fiber.

Claims (8)

1. a kind of alkali metal base cathode, which is characterized in that including alkali metal, and the fluorination carbon materials being uniformly distributed in alkali metal Material.
2. alkali metal base cathode according to claim 1, it is characterised in that:
The alkali metal is selected from least one of lithium, sodium, potassium；
The fluorinated carbon material is selected from fluorinated nano carbon pipe, fluorinated carbon fiber, fluorinated graphene, fluorination hard carbon, fluorination soft carbon, fluorine Change at least one of fullerene, fluorographite.
3. alkali metal base cathode according to claim 1, which is characterized in that in the fluorinated carbon material, fluorine content be 5~ 65%；
The fluorinated carbon material be it is powdered, having a size of 10nm~50 μm.
4. alkali metal base cathode according to claim 1, which is characterized in that the weight of the fluorinated carbon material and alkali metal Than for 1~20:100.
5. alkali metal base cathode described in any claim according to claim 1~4, which is characterized in that the fluorination carbon materials Material is selected from fluorinated nano carbon pipe, fluorinated carbon fiber or fluorinated graphene.
6. a kind of preparation method of alkali metal base cathode described in any claim according to claim 1~5, feature exist In steps are as follows:
1) under inert atmosphere protection, alkali metal is kneaded into flake；
2) carbon fluoride powder uniform load is applied pressure and is allowed to be adhered to alkali metal in alkali metal surface, then through folding With rub pressure after obtain alkali metal base cathode.
7. the preparation method of alkali metal base cathode according to claim 6, which is characterized in that the inert atmosphere is selected from argon Gas, nitrogen or helium.
8. alkali metal base cathode described in a kind of any claim according to claim 1~5 is in alkali metal battery, alkali metal- Application in sulphur battery, alkali metal-air cell.
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CN109841817A (en) * 2019-03-01 2019-06-04 同济大学 For the modification lithium base composite negative pole material of solid state battery and its preparation and application
CN110061308A (en) * 2019-04-16 2019-07-26 浙江大学 A kind of water system battery and preparation method thereof based on cyaniding frame composite material
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CN111564591A (en) * 2020-04-30 2020-08-21 北京航空航天大学 Lithium metal battery diaphragm modified slurry and application thereof
CN112133902A (en) * 2020-10-10 2020-12-25 山东省科学院能源研究所 Sodium metal negative electrode deposition matrix and preparation method and application thereof
CN115159503A (en) * 2022-08-19 2022-10-11 中国科学技术大学 Preparation method and application of carbon material with adjustable degree of order

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