CN109037627B - Alkali metal-based composite negative electrode and application thereof - Google Patents
Alkali metal-based composite negative electrode and application thereof Download PDFInfo
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- CN109037627B CN109037627B CN201810805334.4A CN201810805334A CN109037627B CN 109037627 B CN109037627 B CN 109037627B CN 201810805334 A CN201810805334 A CN 201810805334A CN 109037627 B CN109037627 B CN 109037627B
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- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 98
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 21
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
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- 239000001307 helium Substances 0.000 claims description 2
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- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims description 2
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- 238000007598 dipping method Methods 0.000 claims 1
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 8
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- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- 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
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- 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
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Abstract
The invention discloses an alkali metal-based composite cathode and application thereof, wherein the alkali metal-based composite cathode comprises alkali metal and carbon fluoride material uniformly distributed in the alkali metal; the alkali metal-based composite negative electrode is prepared by a melting infiltration method, and the carbon fluoride material is flatly laid in alkali metal. 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 composite cathode 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 composite negative electrode 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;
the alkali metal matrix composite negative electrode is prepared by a melting infiltration method;
the carbon fluoride material is in a flat state in an alkali metal.
According to the invention, the carbon fluoride material is introduced into the alkali metal by a melting infiltration method 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 dendrite of the alkali metal 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. Further 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. More preferably, the material is a nanoscale material having a size of 10nm to 500 nm. The nano-size is sufficient if the size in at least one direction in the three-dimensional direction is a nano-scale; 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 or graphene fluoride;
the weight ratio of the carbon fluoride material to the alkali metal is 2.5-5: 100.
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 transverse size of the fluorinated graphene powder is 5-50 mu m, the number of longitudinal layers is single layer or few layers (less than 10 layers), and the fluorine content is 50 wt%.
Tests show that the polarization value of a battery assembled by the alkali metal matrix composite negative electrode prepared by adopting the raw materials further optimized can be as low as 22 mV.
Still further preferably, the carbon fluoride material is selected from carbon nanotubes, the alkali metal is selected from lithium metal or sodium metal, and the polarization value can be as low as 20 mV.
More preferably, the carbon fluoride material is selected from carbon fluoride nanotubes, the alkali metal is selected from sodium metal, and the polarization value can be as low as 15 mV.
The alkali metal-based composite cathode is prepared by a simple melting infiltration method, the method is simple in process, the alkali metal is heated and melted only by heating due to the low melting point of the alkali metal, then carbon fluoride powder is added into the melted alkali metal, and the alkali metal/carbon fluoride composite cathode can be obtained by stirring and natural cooling.
The method comprises the following specific steps:
1) under the protection of inert atmosphere, heating and melting alkali metal;
2) and adding carbon fluoride powder into the molten alkali metal, stirring the mixture to be uniform continuously, and cooling and solidifying the mixture to obtain the alkali metal matrix composite cathode.
In the step 1), the inert atmosphere is argon, nitrogen or helium, and preferably argon is used as a preparation atmosphere. The melting temperature is not particularly limited, and is preferably just melting the alkali metal.
In the step 2), the stirring speed is not particularly limited, and it is preferable that the carbon fluoride is uniformly dispersed in the molten alkali metal.
In step 3), the cooling temperature is not specially specified, so that the melt is preferably solidified, and in order to promote the uniform dispersion of the carbon fluoride in the alkali metal, the carbon fluoride can be repeatedly melted and solidified for many times, so-called uniform, and no strict judgment standard exists, and the uniform color is visually observed and microscopic observation is performed under an electron microscope.
The invention also discloses application of the alkali metal matrix composite negative electrode 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 provided by the invention takes alkali metal and carbon fluoride material as raw materials, the carbon fluoride material is uniformly dispersed in the alkali metal by a simple melting infiltration 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 circulation 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 graphene composite negative electrode prepared in example 1;
fig. 2 is a Scanning Electron Microscope (SEM) photograph of the lithium/fluorinated graphene composite negative electrode prepared in example 1;
fig. 3 is a charge-discharge curve of a symmetric battery assembled with the lithium/fluorinated graphene composite negative electrode prepared in example 1;
fig. 4 is F1s X-ray photoelectron spectroscopy (XPS) of the lithium/fluorinated graphene composite negative electrode prepared in example 1 after charging and discharging;
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
Melting metallic lithium by heating under the protection of argon atmosphere; adding fluorinated graphene powder into molten lithium metal, wherein the weight ratio of the weight of the fluorinated graphene to the weight of the lithium metal is 5%, the fluorine content of the fluorinated graphene is 50 wt%, the transverse size of the graphene powder is 5-50 mu m, and the number of longitudinal layers is single layer or few layers (less than 10 layers); and cooling and solidifying the metal lithium melt infiltrated with the fluorinated graphene to obtain the metal lithium/fluorinated graphene composite cathode.
Fig. 1 is an XRD spectrum of the composite negative electrode prepared in this example, and it can be seen from the spectrum that the diffraction peak is a lithium peak, and no diffraction peak appears in the diagram due to low content and low crystallinity of the fluorinated graphene.
Fig. 2 is an SEM photograph of the composite negative electrode prepared in this embodiment, and it can be seen from the photograph that the fluorinated graphene is uniformly dispersed in the lithium metal, and the fluorinated graphene is in a flat state in the alkali metal, that is, the position of the fluorinated graphene is parallel to the lithium sheet, and the fluorinated graphene does not have a local agglomeration phenomenon.
FIG. 3 shows the charge and discharge curves (in LiClO) of a symmetrical battery assembled with a composite negative electrode prepared in this example4The triethylene glycol dimethyl ether (TEGDME) solution is taken as electrolyte, the Celgard C480 membrane is taken as a diaphragm, and when the current density is 0.5mA/cm2Capacity of 1mAh/cm2In this case, the polarization of the symmetrical cell was only 22mV after 200 hours, when the current density was 1mA/cm2Capacity of 1mAh/cm2When 200 hours pass, the polarization of the symmetrical cell is only 91 millivolts, and when the current density is 5mA/cm2Capacity of 1mAh/cm2At 100 hours, the polarization of the symmetric cell was only 292 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 no fluorinated graphene was added to the lithium metal, electrochemical testing showed (current density 0.5 mA/cm)2Capacity of 1mAh/cm2Time, over 200 hours), the polarization was 34 mv, see fig. 5.
Comparative example 2
Electrode preparation and cell assembly as in example 1, except that the same weight was added to the lithium metalElectrochemical tests of amounts of ordinary graphene, but not fluorinated graphene, showed (current density 0.5 mA/cm)2Capacity of 1mAh/cm2Time, 200 hours) and under the same test conditions the polarization was 30 mv.
Comparative example 3
The electrode was prepared and the cell was assembled as in example 1, except that lithium fluoride and graphene were added to the metallic lithium, and the molar amount of fluorine in the graphene and lithium fluoride was the same as that of carbon and fluorine in the graphene fluoride 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 31 mv.
Example 2
The electrode preparation and cell assembly were as in example 1 except that fluorinated graphene was replaced with fluorinated carbon nanotubes 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 20 mv.
Example 3
Under the protection of argon atmosphere, melting metal sodium by heating; infiltrating carbon nanotube fluoride powder into molten metal sodium, wherein the weight ratio of the carbon nanotube fluoride to the metal sodium is 2.5%, and the fluorine content of the fluorinated graphene is 50 wt%; and cooling and solidifying the metal sodium melt infiltrated with the fluorinated carbon nano-tubes to obtain the metal sodium/fluorinated carbon nano-tube composite cathode. The product is characterized by metal sodium by XRD, and the fluorinated carbon nanotube has no diffraction peak in the figure due to low content and low crystallinity. The product is characterized by SEM, and the carbon nano-tube fluoride is dispersed in the metal sodium more uniformly. 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/carbon nanotubes fluoride as electrode was only 15 mV.
Example 4
Under the protection of argon atmosphere, melting the metal potassium by heating; impregnating carbon fluoride powder into molten potassium metal, fluorineThe weight ratio of the chemical carbon fiber to the metal potassium is 10 percent, and the fluorine content of the fluorinated carbon fiber is 50 percent by weight; and cooling and solidifying the potassium metal melt infiltrated with the carbon fluoride fibers to obtain the potassium metal/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 200 hours), the polarization of a symmetrical cell with a potassium metal/fluorinated carbon fiber electrode was only 25 mV.
Claims (7)
1. An alkali metal matrix composite negative electrode is characterized by comprising an alkali metal and a carbon fluoride material uniformly distributed in the alkali metal;
the alkali metal matrix composite negative electrode is prepared by a melting infiltration method; the melting and dipping method comprises the following steps: 1) under the protection of inert atmosphere, heating and melting alkali metal; 2) adding carbon fluoride powder into molten alkali metal, stirring the mixture to be uniform, and cooling and solidifying the mixture to obtain an alkali metal matrix composite cathode;
the carbon fluoride material is in a flat state in alkali metal;
the fluorine content in the carbon fluoride material is 5-65%;
the carbon fluoride material is powdery and has the size of 10 nm-50 mu m;
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.
2. The alkali metal-based composite anode according to claim 1, characterized in that:
the alkali metal is selected from at least one of lithium, sodium and potassium.
3. The alkali metal-based composite anode according to claim 1, wherein the weight ratio of the carbon fluoride material to the alkali metal is 1 to 20: 100.
4. the alkali metal-based composite anode according to any one of claims 1 to 3, wherein the fluorinated carbon material is selected from a fluorinated carbon nanotube, a fluorinated carbon fiber, or a fluorinated graphene.
5. The alkali metal-based composite anode according to claim 4, wherein the weight ratio of the carbon fluoride material to the alkali metal is 2.5 to 10: 100.
6. the alkali metal matrix composite anode according to claim 5, wherein the inert atmosphere is selected from argon, nitrogen or helium.
7. Use of the alkali metal-based composite negative electrode according to any one of claims 1 to 5 in an alkali metal battery.
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