CN109037626B - Alkali metal-based negative electrode and preparation method and application thereof - Google Patents
Alkali metal-based negative electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an alkali metal-based negative electrode and a preparation method and application thereof. According to the invention, the carbon fluoride material is introduced into the alkali metal, the fluoride of the alkali metal can be formed in situ in the charging and discharging processes, the fluoride and the carbon material form a synergistic effect, and a uniform electric field is formed in the charging and discharging processes, so that the uniform deposition of the alkali metal is promoted, the formation of alkali metal dendrites and the interface reaction of the alkali metal and an electrolyte are effectively inhibited, and the safety performance and the cycling stability of the alkali metal battery are improved.
Description
Technical Field
The invention relates to the technical field of energy storage batteries, in particular to an alkali metal-based negative electrode and a preparation method and application thereof.
Background
Although lithium ion batteries still have a leading position in secondary batteries, as new energy automobiles have higher and higher requirements on energy density of lithium ion batteries, the energy density of traditional lithium ion batteries based on intercalation reaction has reached a limit, that is, the energy density of lithium ion batteries with graphite as a negative electrode has approached a bottleneck value, and development of lithium batteries with metal lithium as a negative electrode (including lithium sulfur batteries and lithium air batteries) is imperative. On the other hand, with the development of new energy automobiles, the consumption of lithium resources is fast, but the reserves of lithium on the earth are very limited, and in contrast, the reserves of sodium and potassium are abundant, so that the large-scale use can be met. Therefore, the development of new sodium and potassium based batteries has become a hot spot in current research and development.
However, a fatal problem of a battery using an alkali metal as a negative electrode directly is that the alkali metal forms lithium dendrite during charge and discharge cycles, causing a safety problem of the battery. In addition, alkali metals have poor compatibility with liquid electrolytes and some solid electrolytes, and long-term cycling results in corrosion of alkali metals or formation of interfacial passivation layers, thereby reducing the cycle life of the battery. Therefore, in order to improve the safety and life of the alkali metal battery, it is necessary to perform a protective treatment on the alkali metal.
For example, chinese patent publication No. CN 108063218A discloses a method for preparing a thin-layer metallic lithium-based negative electrode, in which a copper foil current collector is used as a substrate for the negative electrode, a single-layer graphene film is synthesized on the surface of the copper foil current collector by a chemical vapor deposition method, graphene supported by the copper foil is used as a negative electrode, a lithium-rich material or a lithium salt is used as a positive electrode to form a lithium battery, and then a current is applied to deposit lithium in the lithium-rich material or the lithium salt in the graphene supported by the copper foil to obtain a metallic lithium/graphene composite negative electrode The effect of suppressing the reaction with the electrolyte is weak.
Also, for example, chinese patent document with publication number CN 207441857U discloses a metal lithium/artificial inorganic salt composite electrode, which is obtained by depositing an inorganic substance, such as lithium fluoride, lithium bromide, lithium chloride, etc., on the surface of metal lithium by a magnetron sputtering method, and although the method can obtain a relatively uniform surface coating layer, the method is also only suitable for thin electrodes, and is not easy to implement large-scale preparation, and in addition, due to the low conductivity of the inorganic substance, the introduction of a simple inorganic compound causes the decrease of the conductivity of the electrode.
Disclosure of Invention
The invention discloses a novel alkali metal-based cathode which can effectively inhibit the formation of alkali metal dendrites and the interface reaction of alkali metal and electrolyte and improve the safety performance and the cycle stability of an alkali metal battery.
The specific technical scheme is as follows:
an alkali metal-based negative electrode includes an alkali metal and a carbon fluoride material uniformly distributed in the alkali metal.
According to the invention, the carbon fluoride material is introduced into the alkali metal for the first time, the fluoride of the alkali metal can be formed in situ in the charging and discharging processes, and because the fluoride of the alkali metal is in close contact with the carbon material, bonding or partial bonding exists, the fluoride and the carbon material form a synergistic effect, and a uniform electric field is formed in the charging and discharging processes, so that the uniform deposition of the alkali metal is promoted, the formation of alkali metal dendrites is effectively inhibited, and the safety of the alkali metal battery is improved; on the other hand, the fluoride and the carbon material formed in situ can effectively protect alkali metal, inhibit the reaction of the alkali metal and an organic electrolyte or a solid electrolyte, and improve the interface stability of the alkali metal and the electrolyte so as to improve the cycle life of the battery; moreover, the carbon material introduced in situ can improve the conductivity of the composite negative electrode, thereby reducing the polarization of the electrode.
Polarization is the absolute value of the deviation from the origin when the electrode is charged or discharged.
Experiments show that when the technical scheme of directly adding the fluoride and the carbon material is adopted, the fluoride is difficult to realize uniform dispersion in the carbon material and bonding effect of the fluoride and the carbon material, the synergistic effect of the fluoride and the carbon material cannot be realized to inhibit the formation of alkali metal dendrites and protect alkali metals, and the local enrichment of the fluoride with low conductivity also causes the increase of electrode polarization, thereby causing high electrode polarization and short cycle life.
The alkali metal is selected from at least one of lithium, sodium and potassium;
the carbon fluoride material is at least one selected from carbon nano-fluoride tubes, carbon fluoride fibers, fluorinated graphene, fluorinated hard carbon, fluorinated soft carbon, fluorinated fullerene and fluorinated graphite.
Preferably, the weight ratio of the carbon fluoride material to the alkali metal in the alkali metal-based negative electrode is 1-20: 100. in the alkali metal-based cathode, reasonable alkali metal and carbon fluoride contents are beneficial to fully protecting alkali metal without influencing the capacity and the reversibility of the alkali metal cathode. More preferably, the weight ratio of the carbon fluoride material to the alkali metal is 2.5-10: 100. in the alkali metal-based cathode, too low fluorine content is not beneficial to effectively protecting alkali metal, and the conductivity of the composite cathode is reduced due to the lower conductivity of the carbon fluoride, and the conductivity of the composite cathode is reduced due to too high fluorine content, so that the rate capability and the capacity of the cathode are reduced. Preferably, the carbon fluoride material has a fluorine content of 5 to 65%. Based on the commercialization of the carbon fluoride material at present, a commercially available carbon fluoride material having a fluorine content of 50% is directly selected, and in this case, the fluorine content can be adjusted by adjusting the ratio of the carbon fluoride material to the total weight of the raw materials.
Preferably, the carbon fluoride material is in a powder form and has a size of 10nm to 50 μm. Further preferably a nanoscale material having a size of 10nm to 500nm, the so-called nanoscale size being sufficient that the size in at least one direction in the three-dimensional direction is nanoscale; the particles are too small in size and easy to agglomerate, and the particles are too large in size, so that the particles are not beneficial to being uniformly dispersed in alkali metal, and the bonding force between the particles and the alkali metal is weakened.
Preferably, the carbon fluoride material is selected from carbon nanotubes, carbon fibers or graphene fluoride.
Further preferably:
the carbon fluoride material is selected from carbon fluoride nano-tubes;
the weight ratio of the carbon fluoride material to the alkali metal is 2.5-5: 100, respectively; the fluorinated carbon nanotube has a diameter of 30-60 nm and a length of 500 nm-2 μm, and contains 50% by weight of fluorine.
It was found that the polarization value of the cells assembled with alkali metal based negative electrodes prepared with the above further optimized starting materials was only 22 mv at the lowest.
The invention also discloses a preparation method of the alkali metal-based cathode, which takes an industrialized carbon fluoride material as a raw material and is prepared by adopting a simple mechanical mixing method, and the preparation method comprises the following specific steps:
1) kneading alkali metal into a sheet shape under the protection of inert atmosphere;
2) and uniformly loading carbon fluoride powder on the surface of the alkali metal, applying pressure to make the carbon fluoride powder adhere to the alkali metal, and repeatedly folding and kneading to obtain the alkali metal-based cathode.
In the step 1), the inert atmosphere is argon, nitrogen or helium, and preferably argon is used as a preparation atmosphere.
In step 2), the pressure to be applied is not particularly limited, and it is preferable that the carbon fluoride powder is adhered to the alkali metal so as not to fall off.
In the step 3), the number of times of repeated folding and rolling is not particularly specified, and the carbon fluoride powder is preferably uniformly dispersed in the alkali metal, so-called uniform without strict judgment standards, and the color is visually uniform and microscopically observed under an electron microscope.
The invention also discloses the application of the alkali metal-based cathode in an alkali metal battery, an alkali metal-sulfur battery and an alkali metal-air battery.
Compared with the prior art, the invention has the following advantages:
1. the alkali metal-based negative electrode takes alkali metal and carbon fluoride material as raw materials, the carbon fluoride material is introduced into the alkali metal by a simple mechanical mixing method, the fluoride of the alkali metal can be formed in situ in the charging and discharging processes, the fluoride and the carbon material form a synergistic effect, and a uniform electric field is formed in the charging and discharging processes, so that the uniform deposition of the alkali metal is promoted, the formation of dendrite of the alkali metal and the interface reaction of the alkali metal and electrolyte are effectively inhibited, the safety performance and the cycling stability of an alkali metal battery are improved, and meanwhile, the carbon material formed in situ can improve the conductivity and reduce the polarization of the electrode.
2. The preparation process of the alkali metal-based cathode adopts cheap raw materials, has simple process, low energy consumption, low cost and short period, and is beneficial to large-scale production.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the lithium/fluorinated carbon nanotube composite negative electrode prepared in example 1;
fig. 2 is a Scanning Electron Microscope (SEM) photograph of the lithium/fluorinated carbon nanotube composite negative electrode prepared in example 1;
FIG. 3 is a charge-discharge curve of a symmetric cell assembled with a lithium/fluorinated carbon nanotube composite negative electrode prepared in example 1;
fig. 4 is F1s X-ray photoelectron spectroscopy (XPS) after charging and discharging of the lithium/fluorinated carbon nanotube composite negative electrode prepared in example 1;
fig. 5 is a charge and discharge curve of a symmetrical battery assembled with the lithium negative electrode prepared in comparative example 1.
Detailed Description
The present invention is described in further detail below with reference to the drawings and examples, and it should be noted that the following examples are intended to facilitate understanding of the present invention and are not intended to limit the present invention in any way.
Example 1
Kneading the lithium metal into a sheet shape under the protection of argon atmosphere; uniformly loading fluorinated carbon nanotube powder on the surface of the metal lithium, and applying pressure to make the fluorinated carbon nanotube powder adhere to the surface of the metal lithium, wherein the weight ratio of the fluorinated carbon nanotube to the metal lithium is 2.5%, the fluorine content of the fluorinated carbon nanotube is 50 wt%, the diameter of the fluorinated carbon nanotube is 30-60 nm, and the length of the fluorinated carbon nanotube is 500 nm-2 μm; folding and rolling the alkali metal loaded with the fluorinated carbon nanotube powder on the surface, and repeatedly folding and rolling to obtain the metallic lithium/fluorinated carbon nanotube composite cathode.
Fig. 1 is an XRD spectrum of the composite negative electrode prepared in this example, from which it can be seen that the diffraction peak is a lithium peak, and the fluorinated carbon nanotube does not have a diffraction peak in the diagram due to its low content and low crystallinity.
Fig. 2 is an SEM photograph of the composite negative electrode prepared in this example, and it can be seen from the photograph that the fluorinated carbon nanotubes are dispersed in the lithium metal relatively uniformly.
FIG. 3 shows the charge and discharge curves (in LiClO) of a symmetrical battery assembled with a composite negative electrode prepared in this example4The solution of triethylene glycol dimethyl ether (TEGDME) is used as electrolyte, and a Celgard C480 membrane is used as a diaphragm). When the current density is 0.5mA/cm2Capacity of 1mAh/cm2As can be seen from the figure, the polarization of the symmetrical cell was only 22 mV at 200 hours, when the current density was 5mA/cm2Capacity of 1mAh/cm2Polarization of the symmetrical cell is 99 millivolts over 200 hours and symmetrical over 400 hoursThe polarization of the cell was 188 mv.
Fig. 4 is a F1s XPS spectrum of the composite anode prepared in this example after charging and discharging, from which LiF is formed.
Comparative example 1
Preparation of the electrode and assembly of the cell as in example 1, except that fluorinated carbon nanotubes were not added to the lithium metal, electrochemical tests showed that under the same test conditions (current density 0.5 mA/cm)2Capacity of 1mAh/cm2Time, over 200 hours), the polarization was 34 mv, see fig. 5.
Comparative example 2
Preparation of the electrode and assembly of the cell as in example 1, except that the same weight of ordinary carbon nanotubes, instead of fluorinated carbon nanotubes, was added to the metallic lithium, electrochemical tests showed that under the same test conditions (current density 0.5 mA/cm)2Capacity of 1mAh/cm2Time, over 200 hours), the polarization was 28 mv.
Comparative example 3
The preparation of the electrode and the assembly of the cell were as in example 1, except that lithium fluoride and carbon nanotubes were added to the metallic lithium, and the molar amount of fluorine in the carbon nanotubes and lithium fluoride was the same as that in the fluorinated carbon nanotubes in the examples. Electrochemical tests showed that under the same test conditions (current density 0.5 mA/cm)2Capacity of 1mAh/cm2Time, over 200 hours), the polarization was 32 mv.
Example 2
Electrode preparation of electrode and cell Assembly example 1 was followed, except that fluorinated carbon nanotubes were replaced with fluorinated graphite of equal addition and same fluorine content, and electrochemical testing showed that under the same test conditions (current density 0.5 mA/cm)2Capacity of 1mAh/cm2Time, over 200 hours), the polarization was 30 mv.
Example 3
Kneading the sodium metal into a sheet shape under the protection of argon atmosphere; uniformly loading fluorinated graphene powder on the surface of metal sodium, and applying pressure to make the fluorinated graphene powder adhere to the metalOn the surface of sodium, the weight ratio of the weight of the fluorinated graphene to the weight of the metal sodium is 5%, and the fluorine content of the fluorinated graphene is 50 wt%; and folding and rolling the metal sodium loaded with the fluorinated graphene powder on the surface, and repeatedly folding and rolling to obtain the metal sodium/fluorinated graphene composite cathode. The product is characterized by being metallic sodium through XRD, and no diffraction peak appears in the figure due to low content and low crystallinity of the fluorinated graphene. The product is characterized by SEM, and the fluorinated graphene is uniformly dispersed in the metal sodium. Electrochemical tests show that (Current Density 0.5 mA/cm)2Capacity of 1mAh/cm2At 200 hours), the polarization of a symmetrical cell with sodium metal/graphene fluoride as the electrode was only 25 mV.
Example 4
Kneading the metal potassium into a sheet shape under the protection of argon atmosphere; uniformly loading carbon fluoride fiber powder on the surface of potassium metal, and applying pressure to make the carbon fluoride fiber powder adhere to the surface of the potassium metal, wherein the weight ratio of the carbon fluoride fiber to the potassium metal is 10%, and the fluorine content of the carbon fluoride fiber is 50 wt%; and folding and rolling the metal potassium loaded with the carbon fluoride fiber powder on the surface, and repeatedly folding and rolling to obtain the metal potassium/carbon fluoride fiber composite cathode. The product is characterized by metal potassium through XRD, and the fluorinated carbon fiber has no diffraction peak in the figure due to low content and low crystallinity. The product is characterized by SEM, and the fluorinated carbon fiber is uniformly dispersed in the metal potassium. Electrochemical tests show that (Current Density 0.5 mA/cm)2Capacity of 1mAh/cm2At this time, the polarization of a symmetrical cell with the potassium metal/fluorinated carbon fiber electrode was only 32mV over 200 hours.
Claims (4)
1. An alkali metal-based negative electrode for a secondary battery, comprising an alkali metal, and a carbon fluoride material uniformly distributed in the alkali metal;
the carbon fluoride material is a carbon fluoride nano-tube;
the weight ratio of the carbon fluoride material to the alkali metal is 2.5-5: 100, respectively; the diameter of the fluorinated carbon nano-tube is 30-60 nm, the length of the fluorinated carbon nano-tube is 500 nm-2 mu m, and the fluorine content in the fluorinated carbon nano-tube is 50% by weight;
the preparation method of the alkali metal-based negative electrode comprises the following steps:
1) kneading alkali metal into a sheet shape under the protection of inert atmosphere;
2) and uniformly loading the fluorinated carbon nanotube powder on the surface of alkali metal, applying pressure to make the fluorinated carbon nanotube powder adhere to the alkali metal, and repeatedly folding and kneading to obtain the alkali metal-based cathode.
2. The alkali metal-based anode of claim 1, wherein:
the alkali metal is selected from at least one of lithium, sodium and potassium.
3. Alkali metal-based anode according to claim 1, characterized in that the inert atmosphere is selected from argon, nitrogen or helium.
4. Use of an alkali metal-based negative electrode according to claim 1 or 2 in an alkali metal battery, an alkali metal-sulphur battery, an alkali metal-air battery.
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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 |
| CN110061308B (en) * | 2019-04-16 | 2020-10-13 | 浙江大学 | Water-based battery based on cyaniding frame composite material and preparation method thereof |
| CN110137421B (en) * | 2019-05-17 | 2020-08-04 | 中国科学院物理研究所 | Hydrophobic complex film of lithium cell and lithium cell |
| CN110600808B (en) * | 2019-09-20 | 2022-04-12 | 哈尔滨工业大学 | Method for improving lithium dendrite on solid electrolyte interface by using carbon fluoride |
| KR20220091505A (en) * | 2019-10-28 | 2022-06-30 | 성진 조 | Lithium metal anode and manufacturing method thereof |
| CN111564591B (en) * | 2020-04-30 | 2021-10-26 | 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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